Ruthenium: Inorganic & Coordination Chemistry: Sylviane Sabo-Etienne & Mary Grellier

Ruthenium: Inorganic & However, its blue chloride solution had been previously
observed by Vauquelin in Paris in 1804. Ruthenium is the least

abundant platinum metal (103 to 104 ppm) after rhodium.
Coordination Chemistry In 2002, the demand for ruthenium was 11.6 tons, an increase
of 1.8 tons compared to 2001, mainly because of increased
Sylviane Sabo-Etienne & Mary Grellier sales of ruthenium paste to the electronics industry, for the
Laboratory of Coordination Chemistry, Chimie de la Matiere manufacture of chip resistors and hybrid integrated circuits
Condensee (CNRS), Toulouse, France (HIC). Its atomic number is 44, its atomic weight 101.07, and
its electronic configuration [Kr]4d7 5s1 . Seven stable isotopes
Based in part on the article Ruthenium: Inorganic & Coordination are known. Some physical data are reported in Table 1 (see
Chemistry by Bruno Chaudret & Sylviane Sabo-Etienne which Coordination Chemistry: History and Coordination Numbers
appeared in the Encyclopedia of Inorganic Chemistry, First Edition.
& Geometries).
Among the platinum metals, ruthenium shows the largest
1 Introduction 1 range of oxidation states, from II to +VIII, with most of the
2 Ruthenium Halide Complexes 1 inorganic chemistry taking place in the +II and +III states. The
3 Ruthenium Complexes of Oxygen-Donor Ligands 3 chemistry of ruthenium has been comprehensively reviewed
4 Ruthenium Complexes of Sulfur-Donor Ligands 5 in a monograph in 1984 and in Comprehensive Coordination
5 Ruthenium Complexes of Nitrogen-Donor Ligands 6 Chemistry in 1987 and 2003.14 In the most recent review, the
6 Ruthenium Complexes of Phosphorus-Donor results (including osmium chemistry) have been divided into
Ligands 12 two chapters referring to low- and high-oxidation states.3,4
7 Ruthenium Complexes of Group-14 Ligands 16 This article represents an updated version of the one
8 Ruthenium Hydride Complexes 17 published in EIC-1. It is organize in the same way, with
9 Polynuclear Complexes of Ruthenium 19 a survey of the coordination and inorganic chemistry of
10 Related Articles 19 ruthenium, classified by the nature of the ligand, together with
11 References 19
recent highlights in this field. Some old references will not be
quoted and can be found in EIC-1. It is worth noting that the
border with organometallic chemistry remains tenuous (see,
Abbreviations for example, the use of classical coordination compounds for
catalyzing organic reactions; see Ruthenium: Organometallic
acacH = 2,4-pentanedione; BINAP = 2,2 -bis(diphenylphos- Chemistry).
phanyl)-1,1 -binaphthyl; bpy = 2,2 -bipyridine; cod = 1,5-
cyclooctadiene; Cp = cyclopentadienyl; dcype = Cy2 PCH2
CH2 PCy2 ; diop = 2,3-O-isopropylidene-2,3-dihydroxy-1,4-
bis(diphenylphosphinobutane); dmpe = Me2 P(CH2 )2 PMe2 ; 2 RUTHENIUMHALIDE COMPLEXES
DMSO = dimethyl sulfoxide; dpp = 2,9 diphenyl-1,10-
phenanthroline; dppb = Ph2 P(CH2 )4 PPh2 ; dppe = Ph2 Compounds of the formulation RuX3 are known for
P(CH2 )2 PPh2 ; dppm = Ph2 PCH2 PPh2 ; dppp = Ph2 P(CH2 )3 all four halides (X = F, Cl, Br, I). RuCl3 exists as two
PPh2 ; EDA = diazo ethylacetate; edta = ethylenediamine- well-characterized phases (-RuCl3 and -RuCl3 ), which
N ,N ,N ,N -tetraacetate; mnt = 1,2-dicyanoethylene dithi-
Table 1 Selected physical properties of ruthenium
olato; mnts = bis(1,2-dicyano-2-mercaptoethylene)sulfide;
NMO = N -methylmorpholine oxide; pac = polyamino Lattice structure Close-packed hexagonal
carboxylate; phen = 1,10-phenanthroline; phi = phenan Metallic radius for 12-coordination 0.134 nm
threne-9,10-diimine; por = porphyrinato; py = pyridine; Density (20 C) 12 450 kg m3
TEMPO = 2,2,6,6-tetramethylpiperidinooxy; terpy = 2,2 :6 , Melting point 2310 C
Boiling point 3900 C
2 terpyridine; tmbp = 2,2 -Biphosphinines; TMP = tetra Resistivity (0 C) 6.80 cm
mesitylporphyrin; tosyl = p-toluenesulfonyl; tppts = (m- Ionization potential:
NaSO3 C6 H4 )3 P; triphos = MeC(CH2 CH2 PPh2 )3 . 1st 7.364 eV
2nd 16.76 eV
3rd 28.46 eV
96
Ru I = 0 (12.62%)
98
Ru I = 0 (5.51%)
99
Ru I = 0 (1.87%)
1 INTRODUCTION
100
Ru I = 5/2 (12.72%)
101
Ru I = 5/2 (17.07%)
102
Ru I = 0 (31.61%)
Ruthenium was first recognized as a distinct metal in 1844 104
Ru I = 0 (18.58%)
in Estonia by Clauss and was named after Ruthenia (Russia).
Encyclopedia of Inorganic Chemistry, Online 2006 John Wiley & Sons, Ltd.
This article is 2006 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Inorganic Chemistry in 2006 by John Wiley & Sons, Ltd.
DOI: 10.1002/0470862106.ia208
2 RUTHENIUM: INORGANIC & COORDINATION CHEMISTRY
MeCO2H the mixture. We will, nevertheless, refer to the common

MeCO2COMe commercial name throughout this article.
Ru2(O2CMe)4Cl
A large number of mixed-ligand ruthenium(III) halides
acacH, KHCO3 are known. One of the simplest is K2 [RuCl5 (H2 O)],
Ru(acac)3
which is a valuable well-defined RuIII starting material.
A series of dinuclear complexes Ru2 Cl4 (dppb)2 L can be
NH3, Zn
[Ru(NH3)6]Cl2 obtained by electrolysis from the corresponding RuCl3(dppb)L
complexes.5 There is no strong evidence for the existence of
MeCN, any RuX2 complexes. However, reduction of RuCl3 3H2 O
PtO2, H2
RuCl2(MeCN)4 by various reagents (Zn, H2 /PtO2 , Na/Hg, Zn/Hg, etc.) in
alcoholic or aqueous solutions affords a deep-blue solution
C4H6 , ROH (first observed by Vauquelin). The nature of such solutions
RuCl2(C12H18)
is still controversial. Investigations by Rose and Wilkinson
1) CO, ROH in the late 1960s have concluded in favor of the presence of
2) xL the anionic cluster [Ru5 Cl12 ] , although no X-ray evidence
RuCl2(CO)4-xLx
is as yet available on this compound. It was, nevertheless,
1) CO found to be a valuable precursor for the synthesis of a large
MeOCH2CH2OH
2) Zn, EtOH variety of ruthenium (II) derivatives. Bino and Cotton have
Ru3(CO)12 shown that addition of tetraethylammonium chloride to the
cod, EtOH,
deep-blue solution obtained upon dissolving Ru2 (OAc)2 Cl in
[RuCl2(cod)]n 12 M HCl led to a green crystalline material, shown to be the
homoleptic trimer [Ru3 Cl12 ]6 containing Ru(III), Ru(II), and
RuCl3 xH2O

cod, EtOH, Zn, Ru(III) with short RuRu distances (2.805(1) A) in agreement
Ru(cod)(cot)
with single RuRu bonds.
PPh3, EtOH,
RuCl2(PPh3)3
F F
Cp*H, EtOH, H
[Cp*RuCl2]n H
F F
or Me2 Me2 Me2
P P P F
a-phellandrene Ru Ru
[(arene)RuCl2]2 P P P PMe2
Me2 Me2 Me2
arene = benzene, p-cymene
H Me2P
H2, PtO2, EtOH
blue solution (1) (2)
bpy (melt)
Ru(bpy)3Cl2 Some homoleptic fluorides of ruthenium are well char-
bpy, DMF
acterized up to the oxidation state +VI: RuF6 is a volatile
Ru(bpy)2Cl2 dark-brown solid. Mixed-ligand complexes such as RuOF4 are
also known. RuF4 has been isolated by treatment of AsF5 with
[RuF6 ]2 in a HF solution.6 With the other halides, the chem-
Scheme 1 istry starts at the oxidation state IV. RuCl4 can be observed in
the gas phase between 400 and 800 C, whereas the dianions
are prepared by heating ruthenium metal in a stream of MX6 2 (X = F, Cl, Br) are stable. During the last decade,
CO/Cl2 at 600 to 700 C and 330 to 340 C, respectively. considerable progress has been made in the field of tran-
In contrast, the complex commonly known as hydrated sition metal fluoride complexes. Several fluoride(carbonyl)
ruthenium trichloride, or RuCl3 xH2 O, is readily soluble complexes have been characterized (see Carbonyl Com-
in various polar solvents and is commercially available. It plexes of the Transition Metals). A series of bifluoride HF2
is by far the most common starting material in ruthenium complexes incorporating mono- or diphosphines are now
chemistry, whether inorganic or organometallic (see Scheme 1 available.7 In particular, two bifluoride complexes can be
for selected examples of important compounds). However, it isolated from cis-RuH2 (dmpe)2 . The hydride complex trans-
was demonstrated that this species actually corresponds to a RuH(HF2 )(dmpe)2 (1) was obtained by addition of Et3 N3HF
mixture of different ruthenium compounds, mostly in the +IV or by reaction with fluoroarenes as a result of C F activation,
oxidation state. Species such as H3 [Cl3 Ru(-OH)3 RuCl3 ] and whereas reaction with fluoroalkenes produced the fluoride
H3 [Cl3 Ru(-OH)2 (-O)RuCl3 ] have been shown to exist in complex cis-RuF(HF2 )(dmpe)2 (2). The coordination mode of
DOI: 10.1002/0470862106.ia208
RUTHENIUM: INORGANIC & COORDINATION CHEMISTRY 3
the fluoro ligand, terminal versus bridging, plays an important L

role in the stabilization of d6 and d8 complexes.8 O O
O Ru O
O O O
O O
Ru
3 RUTHENIUM COMPLEXES OF OXYGEN-DONOR Ru O O = Carboxylate
O L
LIGANDS (See Water & O-donor Ligands) L OO
O
3.1 Ruthenium Homoleptic Oxo Species (3)

The ruthenium(VIII) complex RuO4 and salts such as
Kn [RuO4 ], derived by reduction (n = 1 3), have been Monooxo and dioxo ruthenium (IV), (V), and (VI)
reported in the literature. However, the compound originally complexes have been extensively studied. Ches group has
thought to be the ruthenium(VI) oxide [RuO4 ]2 has been been very active in this area, and a very detailed analysis of
identified by X-ray crystallography as [RuO3 (OH)2 ]2 . RuO4 this field can be found in the chapter written by Che and Lau
is a yellow, crystalline, low-melting (25.4 C), and highly and published in Comprehensive Coordination Chemistry.4
volatile solid. Care must be taken when using it since it is a The chapter covers the various aspects of the chemistry
highly toxic and powerful oxidizing agent. It reacts explosively (synthesis; characterization, including the Pourbaix diagrams
with a variety of organic solvents. It is, nevertheless, a useful for many representative species; reactivity; and catalysis).
oxidizing reagent for organic substrates such as alcohol, amine, The most important classes of ligands for such Ru(O)n centers
sulfide, and so on. The perruthenate (n Pr4 N)RuO4 salt is a are (1) the porphyrins; (2) the macrocyclic tertiary amine
useful, mild, and selective oxidant of alcohols to aldehydes ligands (see Macrocyclic Ligands); and (3) the pyridine,
or ketones, even in allylic systems. O2 or NMO is used as polypyridyl, and related ligands. Most of the compounds
co-oxidant.9 Interestingly, the salt can be recovered when are very active oxidants for a variety of organic and inorganic
using ionic liquids (see Oxidation Catalysis by Transition substrates.
Metal Complexes).10 The ruthenium(IV) oxide, RuO2 , is a Groves et al. isolated the first dioxoruthenium(VI) por-
stable metallic oxide displaying a low chemical reactivity but phyrin complex Ru(O)2 TMP, able to efficiently catalyze the
aerobic epoxidation of alkenes at ambient temperature and
interesting physical properties. Under high pressure, the rutile
pressure.14 A number of dioxo [Ru(O)2 (por)] and oxo(imido)
form of RuO2 can be converted to a new cubic phase, which
[Ru(O)(por)(NR)] complexes of Ru (VI) with porphyrinato
presents a very low compressibility (comparable to that of
(por) ligands are now available. All these Ru(VI) complexes
diamond).11
are diamagnetic. Complexes incorporating chiral porphyrins
have also been isolated, and for example, enantioselective
3.2 Mixed-ligand Oxo Derivatives aerobic epoxidation of alkenes is achieved by complex (4).
Recent developments involve the design of dendritic ruthe-
The study of mixed-ligand oxo derivatives is closely related nium porphyrins.15 Similar high-oxidation oxo complexes
to the use of these species in catalytic oxidation systems can be prepared using various macrocyclic amine ligands
(including the epoxidation of alkenes and the oxidation such as [14]ane-N4 (5) or 14-tetramethylcyclam (TMC) and
of alkanes. See Oxidation Catalysis by Transition Metal their 15- and 16-member analogs. A cis configuration, as
Complexes). In such complexes, the oxo group can be terminal, in complex (6), can be obtained using a triazacyclononane
doubly bridging, or triply bridging. ligand. (6) oxidizes disubstituted alkynes to 1,2 diketones in
The chemistry of triply bridging oxo(carboxylate) good yields.16
ruthenium clusters of general formula [Ru3 (3 -O)(2 -
O2 CR)6 (L)3 ]n (3) has been extensively developed. A rich 2+ +
chemistry is associated with the strong electronic and magnetic Me
H H Me N
interactions involving Ru(II), Ru(III), and Ru(IV) centers. N
N O N O
They are relevant to biomimetic systems, redox catalysis, and Ru
molecular devices.12 A number of dinuclear ruthenium com- Ru N O
N N Me O
plexes incorporating a bridging oxygen have been isolated and O CF3
H H O
used as a water oxidation catalyst. The -oxo(bipyridyl) dimer
[{Ru(bpy)2 (OH2 )}2 O]4+ (known as blue ruthenium dimer) is
one of the most effective electrocatalytic reagents. The mech- (5) (6)
anism by which it oxidizes water to dioxygen is very complex
(loss of 4e and 4H+ ) and has been extensively investigated Bis-oxo-Ru(VI) complexes containing nonlabile oxidation-
by Meyer et al.13 resistant nitrogen-donor ligands such as pyridine, bipyridine,
DOI: 10.1002/0470862106.ia208
Ru(O2 CCF3 )2 (ROH)2 (PP), incorporating various chiral phos-

phines (PP (diphosphines)), have also been characterized. The
two carboxylates act as monodentate ligands, and two solvent
molecules remain in the coordination sphere of the metal, in
cis positions.19
O
N N Bridging carboxylates are mainly found in three types
Ru of structures: 3 -oxo-bridged trimers, 2 -oxo- or hydroxo-
N
O
N bridged dimers (see Section 3.2), and metal metal multiply
bonded dimers. Diruthenium tetracarboxylates exist as
homovalent Ru2 (II,II) and mixed-valent Ru2 (II,III) species
(see Mixed Valence Compounds). They all adopt the familiar
lantern type motif (see structure (8)). The first dimers
[Ru2 (OCOR)4 Cl] were prepared by reaction of RuCl3 3H2 O
with a mixture of carboxylic acid/anhydride acid. The crystal
(4) structure of [Ru2 (OCOMe)4 Cl] revealed the presence of
infinite chains of Ru2 units linked by Cl. Analogous complexes
terpyridine, and related ligands are another important class can be prepared using a variety of acids. Diadducts of the
of compounds that behave as four-electron oxidants and type [Ru2 (OCOR)4 L2 ]X incorporate L ligands such as H2 O,
convert alcohols to aldehydes or ketones. The remarkable OPPh3 , THF, py, MeOH, and DMSO. The diruthenium
reactivity of high-oxidation-state ruthenium and osmium carboxylate complexes display interesting magnetic and
polypyridyl complexes has been recently reviewed by Meyer electronic properties as potential molecular materials and
and Huynh.17 The polypyridyl species are stronger oxidants liquid crystals. They are now being tested as antitumor
than the macrocyclic family. The chemistry of periodato- drugs.20
derived species has been developed, and for example,
the complex, [Ru(O)2 (bpy){IO3 (OH)3 }] (7), containing the R
triply protonated periodate ligand [I(O)3 (OH)3 ]2 has been R
isolated. (7) behaves as a six-electron oxidant for the OO O O
stoichiometric oxidation of alkenes.18 Chloro and carboxylato
L Ru Ru L
dioxo complexes of Ru(VI) have been prepared and are also
used as oxidants of halides, alcohols, sulfides, and even alkanes O O O O
(see Oxidation Catalysis by Transition Metal Complexes).
R R
(8)
O OH
N O
OH 3.4 Other Oxygen-donor Ligands
Ru I
O O
N O OH Water reacts as a ligand in numerous inorganic and
organometallic compounds. It normally behaves as a
two-electron ligand on one ruthenium center, although some
(7)
rare cases of water bridging two ruthenium centers are
known. The homoleptic ruthenium(III) and ruthenium(II)
3.3 Carboxylate Ligands complexes [Ru(H2 O)6 ]n+ have been known for nearly
40 years. In the course of their studies on Ring Open-
The carboxylate group can act as a three-electron bridging ing Metathesis Polymerization (ROMP) reactions, Grubbs
or chelating ligand, as well as a one-electron monodentate et al. explored the reactivity of [Ru(H2 O)6 ](tosyl)2 with
ligand. This gives rise to a rich chemistry in which inter- acyclic- and monocyclic-functionalized alkenes (L), gen-
conversion between the modes of coordination of the ligand erating monoalkene adducts [Ru(H2 O)5 L]2+ (see Water &
and nuclearity of the complexes is facile. Examples of chela- O-donor Ligands).21
tion are found in the phosphine adducts Ru(OAc)2 (PPh3 )2 Hydroxy ligands generally result from the protonation of
and RuH(OAc)(PPh3 )3 , which are prepared by metathet- oxo or deprotonation of aqua species and are thus found
ical exchange with chloride groups or by protonation of in systems similar to those described above. They occupy
polyhydrides with acetic acid. The dicarboxylate complexes terminal or doubly or triply bridging positions. Alternative
Ru(OAc)2 (BINAP) are at the origin of all the chemistry routes involve the metathetical exchange of Cl by OH
developed by Noyori in asymmetric catalytic hydrogenation or oxidative addition of H2 O. These routes have been used
reactions (see Section 6.2). Similar complexes of the formula by Wilkinson et al. to prepare unsaturated trans hydroxo
DOI: 10.1002/0470862106.ia208
hydrido derivatives such as RuH(OH)(PPh3 )2 (H2 O).1,2 A Cl H 2N NH2 Cl

Cl H2N NH Cl
series of alkoxide and hydroxide complexes have now 2 O Ru
Cl Ru PR3
been designed by Bergman et al., and their properties and Ru Ru R3P O
R3P PR3 PR3
reactivities have been reviewed. The complexes, with a PR3 R3P S S
R3P S S O O
strongly polarized RuO bond, typically display nucleophilic O
reactivity (see Water & O-donor Ligands).22 The formation (9) (10)
of an (alkoxy)ruthenium hydride and a piperidinyloxy species
are postulated in the RuCl2 (PPh3 )3 /TEMPO-catalyzed aerobic
oxidation of alcohols.23 Numerous examples of complexes containing terminal or
Ru(acac)3 is readily prepared from RuCl3 3H2 O, 2,4- bridging thiolato ligands are known. For example, fluorinated
pentanedione, and potassium hydrogencarbonate in hot water. thiolates Ru(II) and (III) species have been prepared in which
Its structure has been determined by X-ray and neutron C6 F5 S acts either as a terminal ligand or as a bridging ligand
diffraction measurements at various temperatures.24 This between two ruthenium centers.28 Trigonal-bipyramidal
compound can be reduced to [Ru(acac)3 ] . Protonation leads Ru(IV) thiolate complexes display a characteristic trigonal-
to liberation of acacH, thus making this compound a suitable planar Ru(SR)3 core, and the organometallic reactivity of these
starting material for ruthenium(III) chemistry. Ru(acac)3 - species is now being explored.29 The homoleptic complex
mediated oxidative di- and trimerization of 1,3-diamino [Ru(mnt)3 ]2 (11) with only sulfur atoms in the coordination
benzene produce new diimine Ru(acac)2 complexes.25 sphere of ruthenium has been isolated. (11) decomposes in
Ruthenium complexes with the bulky N(SPR2 )2 ligand, a the presence of light, leading to the formation of a compound
sulfur analogue of acac, have been synthesized.26 [Ru(mnts)2 ]2 containing a novel tridentate (mnts) ligand.30
Various examples of hydrido(thiolate) complexes have been
reported. Interestingly, protonation can occur at the metal, or
at the hydride to form a dihydrogen complex, or at the sulfur
site to give a thiol complex (see Section 8). The reactivity
4 RUTHENIUM COMPLEXES OF SULFUR-DONOR of the bis(dihydrogen) complex RuH2 (H2 )2 (PCy3 )2 with
LIGANDS (See S-donor Ligands) sulfur heteroaromatic compounds leads to new compounds
presenting different coordination modes of the S-substrates.
Ruthenium sulfur systems have attracted attention, pri- As an example, C S splitting in 2-acetylthiophene results in
marily owing to their relevance to biology and catalysis, the formation of a dihydride metallocycle (12) with a new
in particular, for the hydrodesulfurization process. (see thiolato ligand 2 -(O,S) coordinated to ruthenium.31
Hydrodesulfurization & Hydrodenitrogenation). Soft sulfur
ligands alone cannot stabilize Ru(VI) centers, and no Ru(V)
complexes seem to have been reported with any sulfur lig- CN Me
ands. Sulfide, thiolate, and thioether ligands are unique as they S Me
NC S S CN O
display versatile electronic properties: they can act as pure - Ru Cy3P S
NC S S CN
donors, -donor -acceptors, or even as - -donors because Ru
S PCy3
of their lone pairs (see Subvalent Compounds). The coordi- H
nation chemistry of new mixed-donor ligands is now being CN H
investigated to benefit from the properties of the different (11) (12)
atoms N, P, O, and S (see Sulfur: Inorganic Chemistry).
4.2 Thioethers and Analogous Derivatives

4.1 Sulfides and Thiolato Ligands
Numerous examples of complexes containing thioethers
Ruthenium sulfide (RuS2 ) as well as other chalcogenides have been reported, including the first example by Sellmann
RuX2 (X = Se, Te) adopt a cubic pyrite structure and should et al. of a transition metal compound containing H2 S, namely,
be regarded as Ru2+ (S2 )2 . They are very stable compounds Ru(SH2 )(PPh3 )(S4 ) (S4 = 2,2 -(ethylenedithio)bis(thiopheno-
that are readily prepared by several routes, including direct late)). There is now an example of a room-temperature stable
combination of the elements. The chemistry of ruthenium complex with a P N ligand (see structure (13)).32
complexes with bridging sulfide groups has been particularly The remarkable complexing properties of cyclic thioethers,
examined by Matsumoto et al. The synthesis and properties in particular, those exploited by Schroders and Yoshidas
of a family of complexes with a strong -donor ligand (S2 )2 groups, have stimulated a great interest in metal thioether
bridging two Ru centers have been described. Of particular chemistry. These cyclic ligands bind preferentially to soft
interest is the reaction of (9) with O2 . Amongst other products, metal ions and have allowed the preparation of complexes
oxidation of the sulfide ligand results in the formation of (10) displaying unusual stereochemistry and/or oxidation states.
with a unique bridging S2 O5 2 ligand.27 The most common thioethers involved are [9]ane-S3 ,
DOI: 10.1002/0470862106.ia208
[12]ane-S3 , [12]ane-S4 , [14]ane-S4 , [16]ane-S4 , and [18]ane- in particular as antitumor agents and as radiosensitizers.
S6 . The affinity of ruthenium for these thioethers (see The complex Na{-trans[RuCl4 (DMSO)(Im)]} known as
structure (14)) is evidenced by the loss of arene upon (NAMI), is the first ruthenium compound to enter clinical
reaction of [RuCl2 (arene)]2 with [9]ane-S3 , yielding the trials.3739
homoleptic derivative [Ru([9]ane-S3 )]2+ . Neutral (such RuCl2 (DMSO)4 can be conveniently prepared by refluxing
as [RuCl2 (PR3 )[9]ane-S3 ]), cationic ([RuCl(L1 )(L2 )([9]ane- RuCl3 3H2 O in DMSO for a few minutes. This complex has
S3 )]+ ), or dicationic complexes ([Ru(L1 )2 (L2 )([9]ane-S3 )]2+ ) found wide interest as a starting material, although DMSO
can be prepared as well as dinuclear species.33 is often difficult to eliminate. The sulfoxide ligand has two
possible sites of coordination, sulfur and oxygen. Coordination
to sulfur is generally observed in the case of ruthenium, and
+
the d -S back-bonding plays a major role. S to O linkage
S isomerization was first shown, by Taube et al., to occur
S S
Me2N upon oxidation of [Ru(NH3 )5 (DMSO)]2+ . More recent studies
Cl Cl
Ru Ru demonstrate that DMSO can also be S-bonded to Ru(III)
H2S PPh2 Ph3P and Ru(IV) and suggest that the S-(DMSO) -donation to
N
P(p-tol)3 S Ru is extensive in Ru(II) and Ru(IV) states.40 The complex
[Ru(bpy)2 (DMSO)2 ]2+ is yellow and has two S-bound DMSO
(13) (14) ligands. Upon irradiation, a color change to red is observed,
which is attributed to linkage isomerization from S- to O-
bound DMSO. The yellow color is slowly recovered in the
Sellmann et al. have extensively surveyed the coordination dark.41
properties of tetra- and pentadentate ligands in the search
for reduction of N2 by metal sulfur complexes under
mild conditions (see structures (15) and (16)).34 The RuS4
core is not always preserved and partial cleavage of 5 RUTHENIUM COMPLEXES OF
SC bonds can occur. To circumvent this problem, the NITROGEN-DONOR LIGANDS (See Ammonia &
ethylene bridge in S4 has been replaced by an o-phenylene N-donor Ligands)
bridge.35
Supramolecular chemistry involving transition metal

complexes has received increasing interest over the last
decade. Photo-redox processes for solar energy conversion,
S information storage systems, biosensors, and complexes with
S PPh3 S
Ru H S PPh3 antitumor activity are currently under investigation. In this
S S Ru S
S H S S S S area, the inorganic chemistry of ruthenium, largely dominated
H S S Ru by the chemistry of nitrogen-donor ligands, plays a major role.
H S S Ph3P S
Ru S Several important achievements in inorganic chemistry have
S
Ph3P S involved nitrogen-donor ruthenium derivatives. These include
(1) the first dinitrogen complexes, (2) the Creutz Taube
complex for the study of electron transfer and for the study
(15) (16) of electron transfer in ruthenium-modified proteins, (3) the
photochemistry of [Ru(bpy)3 ]2+ and all the applications of
this and related complexes (from photovoltaic cells to DNA
Pentaammine Ru(III) polarizes thiourea by complexing
intercalation), and (4) the aerobic oxidation of alkenes in
sulfur, and the complex [Ru(NH3 )5 SC(NH2 )2 ](S2 O6 )3/2 H2 O
the presence of ruthenium porphyrin derivatives using both
is isolated. The data are consistent with LMCT from a filled
oxygen atoms.
p sulfur orbital to the vacant dxy -orbital on Ru(III).36
The chemistry of the higher oxidation states is dominated
by metal ligand multiple bonds, with the oxo ligand being
4.3 Sulfoxides the ligand of choice. There are no complexes of Ru(VIII)
and Ru(VII) incorporating an imido or a nitrido ligand
Sulfoxide ruthenium complexes have received attention and almost no Ru(V) compounds. A number of nitrido
in part from the fact that they are useful starting Ru(VI) complexes exist with a variety of ligands, but
materials for new organometallic and coordination compounds the chemistry is much less matured than the analogous
and in part from their role in biology and catalytic osmium chemistry (see Nitrides: Transition Metal Solid-
processes (see Metal-related Diseases of Genetic Origin). state Chemistry). There are no nitrido mononuclear Ru(IV)
Potential applications are found in medicinal chemistry, complexes, but a number of -nitrido species are known.
DOI: 10.1002/0470862106.ia208
The simple amido complex [Ru(NH3 )5 (NH2 )]2+ can be complete blending of oxidation states and the odd electron
easily prepared by deprotonation of [Ru(NH3 )6 ]3+ , and a is delocalized over both sites. The -pyrazine-bridged
series of hydrido(amido) ruthenium complexes have been dimer (17), also named the Creutz Taube ion, was the
recently reported.22 The chemistry of Ru(VI) imido complexes first designed mixed-valence complex. The Nobel prize for
is largely concentrated on oxo(porphyrins) compounds of chemistry was awarded to Taube in 1983 for his work on
general formula Ru(O)(NR)(por). Extensive work on oxo the mechanisms of electron transfer reactions (see Electron
ruthenium(VI) complexes incorporating N-ligands has been Transfer in Coordination Compounds and Electron Transfer
performed, as already mentioned in Section 3.2. Three main Reactions: Theory).13 The electronic structure of (17) has
classes of ligands can be distinguished: (1) the porphyrins, been the subject of numerous studies. The complex is
(2) the macrocyclic tertiary amine ligands, and (3) the considered delocalized but appears to have properties of
pyridine, polypyridyl, and related ligands. The results show both class II and class III in the Robin and Day classification.
a rich electrochemistry, and numerous studies are connected In particular, its spectroscopic properties show some residual
to the use of these compounds as oxidants for a variety localization. It should now be considered as the prototype
of substrates (see Oxidation Catalysis by Transition Metal of a new class of mixed-valence species, Class II III, as
Complexes). Ruthenium porphyrins are efficient catalysts for evidenced by Meyer et al.45 Medium effects on charge transfer
a collection of organic reactions such as epoxidation and in metal complexes have also been reviewed by Meyer et al.46
cyclopropanation of alkenes and hydroxylation and amidation Inventing new analogues of the Creutz Taube ion remains a
of alkanes. For example, a dendritic ruthenium porphyrin very active area of research.47
efficiently catalyzes the EDA cyclopropanation of styrene.15
5+
5.1 Ammine Salts NH3 NH3
NH3 NH3
The hexaammine ruthenium(II) salt [Ru(NH3 )6 ]Cl2 is H3N Ru N N Ru NH3
conveniently prepared by zinc reduction of RuCl3 3H2 O in H3N H 3N
aqueous ammonia. It is readily oxidized in several ways to NH3 NH3
the corresponding ruthenium(III) derivative, [Ru(NH3 )6 ]3+ .
The ruthenium(II) complex is substitutionally very labile,
(17)
unlike the ruthenium(III) analogue, and complexes of
the general formula [Ru(NH3 )5 (L)]2+ display a very rich
photochemistry. [Ru(NH3 )5 N2 ]2+ was the first transition Long-distance intervalence electron transfer is now
metal dinitrogen complex, the discovery of which in demonstrated with metal metal distances up to 25 A. Distance
1965 stimulated the rapid development of nitrogen fixation dependence of electron transfer has strong implications for the
chemistry (see Nitrogenase Catalysis & Assembly). The search of, for example, molecular switch devices or biosensors.
first compound containing a bridging dinitrogen group, The bridging ligand dicyanamidobenzene has been extensively
[(NH3 )5 Ru(N2 )Ru(NH3 )5 ]4+ , was then obtained by mixing studied, and for example, complex (18) exhibits a very strong
[Ru(NH3 )5 N2 ]2+ and [Ru(NH3 )5 (H2 O)]2+ .1,2 Studies on the coupling (0.32 eV) for a metal metal distance of 19.5 A.48
photochemistry of Ru(II) ammine complexes really started in
1969 with molecular nitrogen complexes. The photochemical
reactions are dominated by substitution processes. The 5.2 [Ru(bpy)3 ]2+ and Related Complexes. Some Selected
studies provide a better knowledge into the excited states Applications
reactivity of d6 centers. The properties of the MLCT states
in Ru(II) ammine complexes depend on the nature of the A huge growth has been observed in [Ru(bpy)3 ]2+
L ligand. They can be varied by controlling the acidity of chemistry over the last two decades as the complex displays a
the medium and are solvent dependent. Several investigations unique combination of air and thermal stability and redox
have been focused on the prediction of electronic spectra and photophysical properties (see Electron Transfer in
and on identifying the extent of ruthenium ligand electronic Coordination Compounds and Electron Transfer Reactions:
coupling in mononuclear and dinuclear species. The Theory). More generally, ruthenium complexes incorporating
electronic spectra calculations are performed using modified pyridine or multidentate ligands based on aromatic imines have
INDO/s method (see Photochemistry of Transition Metal attracted more attention than all the other classes of inorganic
Complexes; Photochemistry of Transition Metal Complexes: ruthenium derivatives (see Photochemistry of Transition
Theory).4244 Metal Complexes and Photochemistry of Transition Metal
Mixed-valence complexes exhibit interesting properties Complexes: Theory).3 An exhaustive database of bipyridine-
when significant electron coupling occurs between the donor containing molecules has now been reported.49 Complexes of
and acceptor sites. Most of the systems are Ru(II)/Ru(III) the general formula [RuL6 ]2+ (L = py; L2 = bpy, phen, and
species, but if electronic coupling is sufficient, there is a derivatives; L3 = terpy, etc.) can be prepared by a variety of
DOI: 10.1002/0470862106.ia208
N 3+ [Ru(bpy)3]2+*
0.84 eV 0.84 eV
N
N Ru N [Ru(bpy)3]3+ hn +2.10 eV [Ru(bpy)3]+
N
N 1.26 eV 1.28 eV
C [Ru(bpy)3]2+
[Ru(bpy)3]2+*
N H2O H2 + 1/2 O2
N
Scheme 2
N
C complexes have been assembled by Lehn et al. These rack-
N type structures are based on tridentate ligands with pyrimidine
N and pyridine moieties. A fine tuning of the absorption and
luminescence properties of these complexes can be performed
N Ru N
by introducing substituents on the pyrimidine ring. These
N systems represent key structures for the development of
N photonic and electronic devices.51 The control of the direction
of the energy-transfer process in a multicomponent species
(18) offers new perspectives for artificial functions operating
at the molecular level. The synthesis of multicomponent
systems incorporating Ru(II) polypyridine and anthracene
methods.13 In the case of [Ru(bpy)3 ]2+ , a convenient method chromophores has been performed. The direction of the
involves the reduction of RuCl3 with H2 over Pt black, intercomponent energy-transfer process is reversed on passing
followed by treatment with bpy in MeOH. The red crystals are from room temperature to 77 K.52 Dentritic luminescent
obtained with 80% yield. It is out of the scope of this article structures are now rather common as illustrated by the
to extensively review the photochemistry and photophysics report in Inorganic Synthesis, of a decanuclear ruthenium(II)
studies on [Ru(bpy)3 ]2+ and related species, but we will give polypyridine complex.53,54
a few principles and highlight a few outstanding applications. Incorporation of the Ru(bpy)3 moiety into acyclic,
Many investigations have benefited from the tremendous macrocyclic, and calixarene frameworks leads to a new class of
progress seen in various techniques (such as, for example, anion receptors capable of optical and electrochemical sensing
time-resolved femtosecond absorption spectroscopy). (see (19)).55 The remarkable reactivity of high-oxidation-
[Ru(bpy)3 ]2+ possesses a luminescent excited state, state ruthenium and osmium polypyridyl complexes has
[Ru(bpy)3 ]2+ , which can act as a reducing agent to give been recently reviewed by Meyer and Huynh,17 whereas the
[Ru(bpy)3 ]3+ or as an oxidizing agent to give [Ru(bpy)3 ]+ . significance of polypyridyl complexes as biomimetic models
Therefore, the energy-transfer process may be coupled to for the photosynthetic reaction center was analyzed by Durr
either an oxidizing or a reducing agent. The redox potentials and Bossmann.56 The viologen-linked [Ru(bpy)3 ]2+ system
for couples involving [Ru(bpy)3 ]2+ and the excited state has been widely investigated, and a soluble polymer based
[Ru(bpy)3 ]2+ are shown in Scheme 2. Its redox potentials are on a polypyrrole bisviologen-linked [Ru(bpy)3 ]2+ dyad is
in favor of water splitting. now available. The photostability of the dyad network in the
The design of new molecules, aimed at controlling the presence of oxygen offers new possibilities in photoinduced
transfer of energy and of electrons from the excited state, redox processes (see Electrochemistry: Applications in
is still an active area of research. The current understanding Inorganic Chemistry).57
of electron flow through proteins has been achieved mainly
through the use of photoprobes, with photoactive Ru(II)-
diimine complexes being in widespread use.50 5.2.1 Molecular Photovoltaics
A rich chemistry has flourished in the search for new
luminescent systems (see Luminescence and Luminescence The photochemical properties of bipyridine ruthenium
Behavior & Photochemistry of Organotransition Metal compounds are at the origin of impressive results in
Compounds). A great variety of inorganic architectures have the field of molecular photovoltaics. In 1991, Gratzel
been obtained, including helicates and large multicomponent et al. prepared a molecular photovoltaic system by coating
arrays. As an example, rack-type polynuclear ruthenium TiO2 with a bipyridine complex linked to the surface
DOI: 10.1002/0470862106.ia208
4+ COOH
HOOC
N N COOH
N O O N
N N N N
N H H N NCS
Ru HH N Ru N
N N N HOOC N Ru NCS
N N
O O SCN Ru N
N N COOH
SCN N SCN N
HOOC
(19) COOH
(20) (21)
by carboxylate groups (see Semiconductor Interfaces and

Superconductivity). This system is able to inject one electron component. The design of even more sophisticated molecular-
into the semiconductor conduction band extremely rapidly level machines should open the way to a variety of
after photoexcitation. It is now admitted that the process applications. We have selected three examples to illustrate
occurs in the femtosecond time regime. By contrast, the back this fascinating field.
reaction of the electrons with the oxidized ruthenium complex The design of a rotaxane is a synthetic challenge.
is slow (microsecond to millisecond timescale). This first dye- One strategy is to combine a bifunctional ligand and two
sensitized nanocrystalline solar cell gave a conversion yield of different metals, as demonstrated by Sauvage et al. The
7%. Following this result, hundreds of other complexes have bifunctional ligand containing one dpp and two terpy units
been synthesized and tested, but the polypyridyl ruthenium is treated with a preformed Cu(I)(dpp) macrocyclic complex
complexes remain the precursors of choice for achieving the to afford a prerotaxane complex with pendent terpyridines.
best photovoltaic performances. The best results are now The [Ru(terpy)]2+ is then anchored to the pendent ligands.
obtained by complexes (20) and (21), known as N3 and black Selective removal of the cage Cu(I) template produces the
dye, respectively. The efficiency obtained with the black rotaxane shown as structure (22).61
dye (21) is 10.4% under standard air mass 1.5 reporting Another recent example also comes from Strasbourgs
conditions. The interaction between the carboxylic group and group that prepared the first rotaxane with a [Ru(diimine)3 ]2+
TiO2 is of fundamental importance as the dye is attached via core. The synthetic scheme consists of a threading step fol-
two carboxylates. Projects concerning molecular engineering lowed by a stopping reaction: a ruthenium bisphenanthroline
with judicious substitutions of the carboxylic groups are under complex, acting as an axis, is threaded through a 35-membered
investigation. The ultimate goal is the splitting of water into ring macrocycle incorporating a bpy unit. The pseudorotax-
dihydrogen and dioxygen by sunlight.58,59 In photosynthesis, ane is shown in structure (23). The length of the threaded
water oxidation is accomplished by photosystem II (PSII), ring is too short and an isomer in which the axial ruthenium
which is a large membrane-bound protein. Several studies, complex is attached in an exo fashion is also obtained (see
structure (24)). A modified strategy has allowed the synthesis
aimed at mimicking the light-driven oxidation of water
of a real rotaxane deriving from (23).62
accomplished by PSII, involve the use of a photosensitizer,
The third example comes from Stoddarts and Balzanis
a ruthenium(II) complex incorporating bpy units, linked to
groups. They prepared a photochemically driven molecular-
manganese complexes (see Photosynthesis).60
level abacus by a four-step process. The system is made
up of a photoactive unit P (a [Ru(bpy)3 ]2+ -type complex
5.2.2 Molecular Machines serving as a stopper), two different -electron acceptors A1
and A2 playing the role of stations for a -electron-donor
A special issue devoted to molecular machines appeared ring R (the BPP34C10 macrocycle), a rigid spacer S, and a
in Accounts of Chemical Research in 2001. It reflects the tetraarylmethane group as second stopper T. The [2]rotaxane
current interest for this field in which ruthenium complexes is shown as structure (25). The photochemically driven
act as important tools. Molecular machines are characterized switching of the ring R between stations A1 and A2 is achieved
by a mobile part and a stationary part. Photochemical and by a mechanism involving a sacrificial electron donor.63,64
electrochemical inputs can make a machine work, offering the
advantage of being switched on and off easily and rapidly. 5.2.3 Interaction with DNA
Mechanically interlocked molecules, such as rotaxanes and
catenanes, are suitable candidates. Crown ethers, cyclophanes, Transition metal complexes can help target DNA
and calixarenes are representative families of the cyclic sites with specificity, probe DNA, and furnish highly
DOI: 10.1002/0470862106.ia208
4+ 2+
OCH3
N N
O
O
O
O
N
N N
N
O N
Ru
O N
O N
O O N
O O
O O
N N
N N OCH3
N Ru N N Ru N
(23)
N N
N N
2+
OCH3
Me Me
(22)
sensitive diagnostic agents. Metallointercalators contain O O O

planar aromatic heterocyclic groups able to insert and N
stack between the base pairs of double helical DNA N N
(see Intercalation Chemistry and Nucleic AcidMetal Ion Ru N
Interactions). Extensive work was performed by Barton N
et al., and key features on recognition and reaction of N
O O O
metallointercalators with DNA have been reviewed in 1999.65
One of the earliest examples concerned [Ru(phen)3 ]2+
existing, like any tris(diimine) ruthenium complex, as a
mixture of enantiomers. In order to improve the complex
binding affinities for DNA, the search for new ligands favoring
intercalation was undertaken. Structures (2628) are some
typical examples. Minor changes in the ligand architecture OCH3
(24)
and electronic structure can lead to profound influences on
binding geometries.
The data concerning [Ru(phen)2 (dppz)]2+ nicely illustrate DNA bases is also obtained by electrochemical activation of
the concept of molecular light switch (dppz for 28). When [Ru(bpy)3 ]2+ . Recent developments concern the damage to
the complex is bound to DNA, the excited-state lifetime DNA sites from a distance: site damage up to 200 A away
is approximately 200 ns, whereas without bounding, it is from the site of intercalation of the metal oxidant has been
only 200 ps. This light-switch effect provides the basis for a reported (see Long-range Electron Transfer in Biology).
valuable photophysical probe of nucleic acids. Luminescent One of the main challenges now is to use these molecules in
characteristics of the complexes bound to DNA can also vivo.65,66
be used to illustrate the chiral discrimination associated The synthesis and properties of Ru(II) nucleosides and
with binding to the right-handed helix. Direct oxidation of oligonucleotides have been recently reported using solid-phase
DOI: 10.1002/0470862106.ia208
P S A2 A1 R T
N+
O
N+ O
O N+ O
N
N N O O
Ru O N+
N N O
N O O O
O
(25)
reduction of coordinated nitric oxide. For example, Shepherd

et al. have studied, for the first time, a series of NO+ , NO ,
N N N N N
and NO [Ru(hedta)]n complexes by keeping a constant
ligand metal environment (see structure (29)). They found
N N N N N that the metal remained in the same oxidation state (II).68
The most common geometry displayed by ruthenium
nitrosyl complexes is octahedral. However, some square-
(26) (27) (28) pyramidal and sawhorse geometries have been characterized.
Chloride abstraction from Ru(NO)Cl(CO)(PR3 )2 presenting
phosphoramidite chemistry. The first results offer interesting a square-pyramidal geometry leads to [Ru(NO)(CO)(PR3 )2 ]+
perspectives.67 (30) with a sawhorse structure, as a result of an intramolecular
redox process. NO bending modification, from bent to linear, is
concomitant with a formal decrease in the ruthenium oxidation
5.3 Nitrosyl Ligands state from +II to 0.68 [Ru(NO)2 Cl(PPh3 )2 ] PF6 was the first
complex containing the two modes of binding, that is, linear
The nitrosyl ligand can be combined with any other ligand and bent (RuNO axial, 138 RuNO equat, 178 NO
(X, OH, H2 O, CO, PR3 , acac, NH3 , cyclam, N -aromatic linear, 1845 cm1 ; NO bent, 1687 cm1 ).
heterocycles, NO2 , SO2 , DMSO, etc.) to form a wide range of
nitrosyl ruthenium compounds (neutral, cationic, and anionic)
with linear or bent NO ligands. This has been recently reviewed O
by Legzdins et al. and Housecroft.3,68 The organometallic
chemistry of nitrosyl ruthenium complexes is very rich, and O +
O
various alkyl, acyl, alkene, carbene, and allyl complexes are tBu)
N O PMe( 2
known (see Nitrogen Monoxide (Nitric Oxide): Bioinorganic Ru CO
Ru
Chemistry and Ruthenium: Organometallic Chemistry). The N NO
ON
last decade has seen a renewed interest in understanding O PMe(tBu)2
the chemistry of metal nitrosyl complexes, owing to the
participation of NO in a wide range of physiological processes. OH O
The coordination and the release of NO by ruthenium (29) (30)
dimethylsulfoxide39 and ruthenium amine69 complexes have
been extensively investigated. Techniques such as X Ray, 15 N
NMR, IR, EPR are very useful for determining the mode of 5.4 Miscellaneous Nitrogen Ligands
bonding (i.e. N is deshielded by up to 450 ppm in bent form
as compared to linear NO ligands). Spectroscopic methods Although they have not yet attracted as much attention as
associated with electrochemical techniques lead to a better the nitrosyl complexes, a large number of the isoelectronic
understanding of the NO release mechanism. Studies of the thionitrosyl ones have been prepared. The most representative
reactivity of nitrosyl complexes are oriented toward reactions family is Ru(NS)Cl3 L2 , where L is phosphines, arsines, or
involving oxygen transfer to or from nitrosyl ligands and stilbines. A linear bonding mode is observed.
DOI: 10.1002/0470862106.ia208
We have previously mentioned in Section 4.2 the chemistry absence of protonation by acids. A series of substituted
developed by Sellmann et al., by using tetradentate or complexes [Tp*RuH(H2 )L] could be obtained (L = PCy3 ,
pentadentate S4 ligands. The use of such a ligand in tetrahydrothiophene (THT), py, NHEt2 ). (32) catalyzes the
nitrosyl ruthenium chemistry allowed the first conversion reduction of ketones in mild conditions either by H2 or by H2
of a nitrosyl complex into a ruthenium HNO complex (31) transfer from alcohols.74 Cationic Tp complexes of the general
by addition of NaBH4 to [Ru(NO)(pybu S4)]Br. The formation formula [TpRu(H2 )LL ]+ were obtained by protonation of
and decomposition of HNO complexes is often invoked in the corresponding hydrides.76 TpRuCl(cod) is a precursor of
many processes such as combustion of fuels, oxidation of N2 , choice for inducing a rich organometallic reactivity, which
reduction of HNO2 , and so on.70 has been reviewed. Tp complexes accommodating carbon
single or double bonds have been obtained and various
catalytic coupling reactions were performed.77 Another
precursor of choice is TpRuCl(PPh3 )2 , whose synthesis has
been described in Inorganic Synthesis.78 BpRuH(cod) is
N a valuable precursor for a series of bispyrazolyl BpRu
S S complexes in which the Bp ligand is able to coordinate
Ru with the ruthenium using three different modes: 3 (N ,N ,H),
S S 2 (N,H), or 2 (N ,N ).79
N
H O
(31) H R R
R N N
B N
R N
A large number of compounds with N-donor hetero- B N
N N N
N R
cyclic ligands have been prepared. Ruthenium complexes N N R
N H
incorporating phthalocyanine or aza-macrocyclic ligands are R
known (see Macrocyclic Ligands). In comparison to por- R
R H Ru Ru
phyrin chemistry, metallosalens and metallosalophens have H Me3P
received little attention, despite an easier synthetic access. A H H H
series of mononuclear and binuclear ruthenium derivatives H
with N2 O2 Schiff base ligands are available. Some of them (32) (33)
can act as supramolecular synthons.71 -Amino acids stabi-
lize Ru(bpy)2 moieties to produce the corresponding cations.
The amino acid acts as a bidentate N,O-donor, leading to a Nitriles, specifically acetonitrile, play an important role as
five-membered metallocycle. A six-membered imine Ru(III) solvents in inorganic chemistry. Nitriles are therefore found as
metallocycle was obtained by reduction of an oxime with
co-ligands in various ruthenium complexes. [RuCl2 (MeCN)4 ]
RuCl2 (PPh3 )3 .72
is readily prepared by reduction of RuCl3 3H2 O in acetonitrile
The chemistry of ruthenium complexes incorporating edta,
using different methods, a convenient one being the use of
or related ligands such as pac, is generally based on substitution
dihydrogen and Adams catalyst (PtO2 ). This complex is an
reactions of the water ligand present in the coordination sphere
excellent well-defined ruthenium(II) starting material.
of the metal. The catalytic properties of these complexes
in various organic transformations have been exploited,
including electrocatalytic studies.73
The trispyrazolyl borate chemistry (see BoronNitrogen
Compounds) of ruthenium has prospered mainly during the 6 RUTHENIUM COMPLEXES OF
last decade and is mostly restricted to ruthenium (II). The PHOSPHORUS-DONOR LIGANDS (See P-donor
most common coordination mode of the tripyrazolylborates Ligands)
(Tp) ligand is the 3 (N ,N ,N ) mode (see structure (32)),
but there are also some examples of the 3 (N ,N ,H ) and
2 (N,H) (see structure (33)) modes.74,75 Two principal areas The chemistry of ruthenium (II) complexes incorporating
have been explored: the search for new polyhydrides and the P-donor ligands, particularly phosphines and diphosphines,
organometallic reactivity of TpRu precursors. A rare example is flourishing. This class of compounds has given rise to a
of a stable bis(dihydrogen) complex Tp*RuH(H2 )2 (32) could versatile organometallic reactivity. They are also found in
be isolated. Its chemistry is dominated by the electrophilic many catalytic cycles, but decoordination of the phosphine
character of the hydride and dihydrogen ligands, as illustrated from the coordination sphere of the metal is often required for
by the rapid exchange in deuterated solvents or by the the catalysis to proceed.
DOI: 10.1002/0470862106.ia208
PF3 has found wide use as a precursor for other ruthenium(II)

RuCl2(PPh3)2(PF3)2 complexes and as a catalyst precursor for various reactions,
essentially associated with hydrogenation or hydrogen
PEt3 transfer (see Hydrogenation & Isomerization of Alkenes).
RuCl2(PR3)4
RuCl2 (PPh3 )3 can undergo three types of elementary reactions:
PR3 (1) nucleophilic substitution of chloride groups, (2) addition
(R = Me, OPh) of two-electron donor ligands, and (3) substitution of
RuCl2(PEt3)3
triphenylphosphine ligands and, usually, a combination of the
Py three of them. Selected examples are shown in Scheme 3.
RuCl2(PPh3)3(py) The structure of (34) can be considered as octahedral,
one hydrogen atom of a phenyl ring of a phosphine
DMSO occupying the vacant coordination site. However, the RuH
RuCl2(PPh3)(DMSO)3
distance is long (2.59 A), indicating a very weak agostic
RuCl2(PPh3)3
[16]ane-N4
RuCl2([16]ane-N4)
interaction. Additional structural information can be gained
on (34) and related complexes by 31 P CP/MAS NMR
RCN spectroscopy.80 It is remarkable that the use of ortho-methyl
RuCl2(PPh3)2(RCN)2 substituents has allowed the isolation of the first complex
RCHO with two Ru HC agostic interactions RuCl2 {PPh2 (2,6-
RuCl2(PPh3)2(CO)
Me2 C6 H3 )}2 (35), as demonstrated by NMR and X ray.81
CO RuCl2 (PPh3 )3 was one of the first transition metal complexes
RuCl2(PPh3)2(CO)2
shown to activate dihydrogen heterolytically. The mechanism
Na(S2CNR2) involves deprotonation from a transient unstable dihydrogen
Ru(S2CNR2)2(PPh3)2 complex (see Dihydrogen Complexes & Related Sigma
TCNQ
Complexes). As shown in Scheme 3, some or all of the
[Ru(TCNQ)(PPh3)2]2 phosphine ligands can be substituted by various ligands. This
Na(C5H5)
includes diop, which leads to [{RuCl2 (diop)}2 (-diop)], and
RuCl(h5-Cp)(PPh3)2 various bidentate phosphines (L2 ), leading to complexes of
the general formula RuCl2 L2 (PPh3 )2 or RuCl2 (L2 )2 .
P(OPh)3, H2
RuHCl[P(OPh3)3]4
PPh3
CO
Cl PPh3 Me Cl Me
RuHCl(PPh3)2(CO)2
Ru Ph2 Ph2
Ph2P Cl P P
P(2-C5H4N)3 Ru
RuHCl[P(2-C5H4N)3]3 H
RuHCl(PPh3)3 H2C H H CH2
KOH, H2O Cl
RuH(OH)(PPh3)2(H2O)
(34) (35)
LiN(SiMe3)2
RuH[N(SiMe3)2](PPh3)2
Phosphine substitution by water-soluble ligands has been
HSi(OEt)3 used for the design of new catalysts that could be recovered
RuH[Si(OEt)3](PPh3)3 from the aqueous phase. Extensive intra- and intermolecular
hydrogen bonding are responsible of the high water
Scheme 3 solubility of a secondary tertiary hydroxymethylphosphine
complex, [Ru{P(CH2 OH)3 }2 {P(CH2 OH)2 H}2 Cl2 ].82 The most
important class of water-soluble ligands incorporates sodium
6.1 Triphenylphosphine Derivatives sulfonate groups, with tppts being the preferred ligand. The
complexes RuCl2 (tppts)3 , [RuCl2 (tppts)2 ]2 , RuHX(tppts)3
The most important phosphine derivative of ruthenium (X = Cl, I, OAc), and RuH2 (tppts)4 can be prepared, and
is RuCl2 (PPh3 )3 (34), which is readily prepared from these display a reactivity in water similar to that of
RuCl3 3H2 O and PPh3 in methanol. This procedure is, triphenylphosphine complexes in organic solvents, with,
however, not generally used since large basic phosphines in some cases, an increase in activity and enhanced
(Pi Pr3 , PCy3 ) lead to alcohol decarbonylation, whereas regioselectivity.83
trichloro-bridged ruthenium(III) dimers are obtained by using The reaction of RuCl2 (PPh3 )3 with diphenylcyclopropene
small basic phosphines such as PMe2 Ph. RuCl2 (PPh3 )3 (34) led to the isolation of the alkylidene complex, whereas
DOI: 10.1002/0470862106.ia208
addition of an aryldiazoalkane allowed the formation of Chatt et al., a wide range of cis and trans RuX2 (LL)2 com-
the benzylidene catalyst (see Scheme 4). These complexes plexes have been synthesized by the reaction of RuCl3 3H2 O,
are the first members of the L2 X2 Ru=CHR family RuCl2 (PPh3 )3 , RuCl3 (py)4 , or K2 RuCl5 (OH2 ) with LL in
that has led to impressive developments, mainly by R. alcoholic solution (LL = dppm, dppe, dppp, dmpe, etc.).
Grubbs group, in the field of olefin metathesis (see Elegant studies involving laser flash photolysis and matrix
Carbene Complexes; Metathesis Polymerization Processes isolation show the importance of RuH2 (LL)2 complexes
by Homogeneous Catalysis; Organic Synthesis Using in CH bond activation. Dihydrogen loss and formation of
Metal-mediated Metathesis Reactions, and Ruthenium: square-planar Ru(LL)2 intermediates are induced by photol-
Organometallic Chemistry).84 ysis (see Photochemistry of Transition Metal Complexes and
RuCl2 (PPh3 )3 and RuHCl(PPh3 )3 display a large catalytic Alkane CarbonHydrogen Bond Activation).86 A few ruthe-
activity. RuHCl(PPh3 )3 is one of the most active alkene hydro- nium complexes incorporating trans-spanning diphosphine
genation catalysts, while RuCl2 (PPh3 )3 is of special use for ligands have been synthesized. However, the advantages of
hydrogen transfer reactions, in particular, the hydrogenation using such peculiar ligands remain to be demonstrated.87
of bulky or functional compounds (equation 1) (see Hydro- The most significant industrial applications come from
genation & Isomerization of Alkenes). RuCl2 (PPh3 )3 is also Noyori et al., who have described ruthenium complexes
a catalyst for hydrosilation (see Hydrosilation Catalysis), bearing chiral BINAP ligands (see Asymmetric Synthesis by
although it is slow; chlorocarbon addition to alkenes; and Homogeneous Catalysis).88,89 Noyori shared the Nobel Prize
even oxidation. for chemistry in 2001 with Knowles and Sharpless for his
achievements in asymmetric catalysis. BINAP Ru dihalide
RRCHOH + MeCH=CMeCO2H catalysts have a very wide scope in industrial applications.
RuCl2(PPh3)3 The first key complexes, (36) and (37), were obtained in good
(1)
yield by the reaction of [RuCl2 (cod)]n with (S)-or (R)-BINAP
RRCO + MeCH2CHMeCO2H and triethylamine at 110 C, followed by final treatment with
sodium acetate in t-butyl alcohol at 80 C. The crystal structure
of [Ru(OCO-t Bu)2 {(S)-BINAP}] indicates a C2 chirality.
6.2 Diphosphine Complexes They are very effective catalysts in the hydrogenation of
alkenes or ketones (see Hydrogenation & Isomerization of
A large number of bidentate phosphine ligands accommo- Alkenes). For example, the synthesis of the anti-inflammatory
date ruthenium in various oxidation states and in mono- or drug Naproxen is achieved quantitatively in 97% optical yield.
dinuclear structures. Some can be found in the same com-
plex as both a monodentate and a bidentate ligand. The
number of Ru(III) complexes is rather limited, but a series of
RuCl3 (PP)L complexes have been prepared with PP = dppb
or diop. In the case of L = H2 O, the X-ray structure shows
PAr 2 O PAr 2 O
that the aqua ligand forms hydrogen bonds with two chloro O
O Ru
ligands of a neighboring molecule (see Hydrogen Bonding Ru O
O
& Dihydrogen Bonding). The exchange coupling between PAr 2 PAr 2 O
O
the two Ru III centers is evidenced by ESR data.85 The
most important family is represented by complexes of the
general formulation RuX2 (LL)2 . Since the earlier work by
(36) (R)-BINAP Ru II complex (37) (S)-BINAP Ru II complex
Ph
PPh3
Ph Cl These Ru-catalysts provide a practical way to prepare
Ru Ph an intermediate for prostaglandin synthesis. Antibacterials
Cl and carbapenem antibiotics are now produced industrially.
PPh3 Ph
New achievements have been obtained with the introduction
RuCl2(PPh3)3 of diamine ligands, leading to the asymmetric synthesis of
PPh3 various pharmaceutical compounds. The catalyst mixture,
Cl as shown in Scheme 5, consists of a complex of the
Ru
Ph form RuCl2 (diamine)(diphosphine) with an alkoxide base,
N2 Cl
Ph
PPh3
dihydrogen, and ketone in 2-propanol (see Asymmetric
Synthesis by Homogeneous Catalysis).88,89 An in-depth
mechanistic study was performed by Morris group, leading
Scheme 4 to a better understanding of the catalytic cycle as depicted
DOI: 10.1002/0470862106.ia208
O OH (PP3 = P(CH2 CH2 PPh2 )3 ) was used as an entry to mono- and

polyhydride ruthenium(II) complexes. The Ru (II) complex
(S, SS)-[Ru] [(triphos)RuH(BH4 )] with the tripodal ligand triphos reacts
+ H2
(CH3)2CHOH with KOt Bu to form the ruthenate complex [K(triphos)RuH3 ].
45 atm
30 C, 48 h The compound catalyzes benzothiophene hydrogenolysis into
S/C 2 400 000/1 80% ee, 100% 2-ethylthiophenol.92 Various ruthenium complexes containing
TOF = 63 s1 a triphosphine ligand deriving from PPh(CH2 CH2 PR2 )2 and
PPh(CH2 CH2 CH2 PR2 )2 have been prepared, including chiral
ligands. The ability of the polydentate phosphine to control
(S, SS)-[Ru]: the stereochemistry and coordination number of the resulting
Cl complexes, and the presence of hydride and/or dihydrogen
PAr 2 NH2 ligands provide access to unusual chemical (homogeneous
Ru + (CH3)3COK
catalysis) and structural properties.93 A series of complexes
PAr 2 Cl NH2 incorporating a rigid allene-bridged polyphosphine exhibit
room-temperature luminescence.94
During the past decade, the chemistry of complexes
Ar = 4-CH3C6H4 incorporating phosphine-based pincer ligands has rapidly
developed. Most of these ligands are cyclometalated and
thus will not be reviewed in this chapter. However, various
Scheme 5
complexes incorporating PNP ligands have been prepared
and show interesting spectroscopic and catalytic properties
O (see PhosphorusNitrogen Compounds).3,95,96 The reactivity
of the ligand (R2 PCH2 SiMe2 )2 N on ruthenium has now
H H appeared. The most striking result is the characterization of
H H a four-coordinate, planar Ru(II) displaying a triplet state as a
P NH P NH
Ru Ru consequence of the low-coordination number and the lack of
agostic interactions (see structure (38)).97
P NH P NH2
H H 2,2 -Biphosphinines (tmbp) are analogous to bipyridines,
H albeit containing two phosphorus atoms (see Phosphorus:
Organophosphorus Chemistry). These ligands behave as
R excellent acceptors, and chloro ruthenium complexes
R1 * OH
H
incorporating one or two tmbp could be isolated. The most
significant result was obtained using the reduced ligand,
H H and stabilization of a dianionic Ru complex was achieved.
P NH P NH The complex [Ru(tmbp)2 ][Li(THF)3 ]2 (39) presents a square-
H2
Ru Ru planar geometry with electrostatic interaction between Ru and
P NH H2 P NH2 Li centers.98
H H
H
Scheme 6 O O
O
Me2Si PtBu2 Li+
90 P 2 P
in Scheme 6. The use of the water-soluble dibenzofuran- N Ru Cl Ru
based diphosphine ligands (BIFAPS) leads to high ees in Me2Si P P
PtBu2 Li+
Ru-catalyzed hydrogenations (similar to BINAP).91 O
O O
6.3 Polydentate Phosphines, Pincer Ligands,

Phosphorus Heterocycles, and Phosphorus-based (38) (39)
Hemilabile Ligands
The use of polydentate phosphines has received a renewed The synthesis of hemilabile ligands for the design of
interest, with the search for new families of polyhydrides or new catalysts is a very active area of research. Hemilabile
molecular dihydrogen complexes (see Dihydrogen Complexes ligands act as chelating ligands with one strongly and one
& Related Sigma Complexes). For example, PP3 RuCl2 weakly bonding group (see Structures (40) and (41)). The
DOI: 10.1002/0470862106.ia208
weakly bonding group can be easily displaced, offering bonds) can also be isolated.101 The factors that promote the
new opportunities for catalytic applications. In this context, formation of the different structures are multiple, and the
the chemistry of mixed phosphorus chelating ligands has substituents on silicon and the electron density on ruthenium
been particularly examined (see Mixed Donor Ligands). play a crucial role. Ruthenium complexes incorporating one,
The most common type concerns the phosphorus oxygen and even two, -SiH bonds are now available, as shown by
association, while systems with phosphorus sulfur or the general structure [RuH2 {(2 -HSiR2 )2 X}(PCy3 )2 ] (43).104
phosphorus nitrogen ligands are more limited. A common It is important to note that in these bis(silane) complexes, the
reaction involves PPh3 substitution by the hemilabile ligand L establishment of secondary interactions between the silicon
from RuCl2 (PPh3 )3 or from RuHCl(PPh3 )3 .99 atoms and the classical hydrides stabilize the complexes and
promote the unusual cis position of the bulky phosphines.105
H
O PMe3 R2Si H
Ph2P Ph2P H
OH Ph3P Me3P H PCy3
N Ru SiR3 Ru
O O O O Ru R3Si
Cl O H H PCy3
Ru Cl PMe3 R2Si H
P P
HPh2 Ph2
(42) (43)
(40) (41)
Unusual redistribution at silicon is observed by
adding secondary silanes to the bis(dihydrogen) com-
plex RuH2 (H2 )2 (PCy3 )2 (see Section 8).106 The complex
[RuH2 (PR3 )2 ]2 (-2 : 2 : 2 : 2 -SiH4 ) (44) (R = Cy, i Pr)
7 RUTHENIUM COMPLEXES OF GROUP-14 is isolated with the SiH4 ligand trapped in between the
LIGANDS two metals. The silane is coordinated to the metals via
four -SiH bonds. Each interaction involves -donation
Carbonyl complexes and complexes incorporating iso- to a ruthenium and back-bonding from the other ruthenium.
cyanides are generally considered to be organometallic and are A second redistribution process is observed after addition
not reviewed in this article (see Ruthenium: Organometal- of an excess of HSi(OMe)3 to (44). The dinuclear com-
lic Chemistry and Carbonyl Complexes of the Transition plex (45) is isolated, and the data show that the frontiers
Metals). In contrast, cyanides are regarded as inorganic com- between true -RuHSi interactions and more delocalized
plexes (see Cyanide Complexes of the Transition Metals). systems are not clear-cut (see Scheme 7).106 Silyl and -silane
K4 [Ru(CN)6 ] was first prepared in 1896 through the action of complexes find important applications as catalyst precursors
KCN on K2 [RuO4 ] or RuCl3 xH2 O. Hexacyanide is found as for SiC coupling in hydrosilylation, dehydrogenative silyla-
a tetraanion with various cations or even as the tetracid. This tion, and dehydrocoupling for the formation of vinyl silanes
complex undergoes a variety of substitution reactions and and oligomeric carbosilanes, respectively (see Hydrosilation
gives rise to cyano-bridged polynuclear compounds, either Catalysis; CarbonCarbon & CarbonHeteroatom Activa-
homo- or heteronuclear. Among the substitution reactions, a tion, and Polysiloxanes & Polysilanes).
lot of interest has been devoted to the photophysical properties In comparison to Si, much less work has been published
of mixed cyanide/diimine complexes.100 concerning Ge or Sn (see Germanium: Organometallic
Silane activation by ruthenium complexes has been a Chemistry and Tin: Organometallic Chemistry). The complex
field of intense activity over the past decade. This was Ru(GeMe3 )2 (PMe3 )4 is an effective catalyst for the production
made possible thanks, in particular, to the fantastic progress
achieved in NMR and X-ray techniques, as well as in DFT
(OMe)2
calculations. A number of ruthenium complexes incorporating (MeO)2Si Si
a silicon-attached ligand (see Silicon: Inorganic Chemistry) PCy3 Cy3P H H
H H H H
are now available, with several variations of interactions H H (MeO)3SiH
Ru Si Ru Cy3P Ru Ru PCy3
between the silane and the metal.101 Full oxidative addition H H Si(OMe)4
H H H
can be observed leading to SiH bond breaking and formation PCy3 H H H
PCy3
of the corresponding silyl or bis(silyl) complexes (42).102 Si
(OMe)2
Arrested addition leads to the isolation of -silane complexes,
(44) (45)
analogous to the -dihydrogen complexes (see Dihydrogen
Complexes & Related Sigma Complexes).103,104 Bridging
and terminal SiR2 groups (silylene complexes with Ru=Si Scheme 7
DOI: 10.1002/0470862106.ia208
of high molecular weight polygermanes from HGeMe3 .107 A a dihydrogen formulation. In addition, many more the-
number of complexes incorporating the RuSnR3 moiety have oretical studies are now performed on polyhydrides and
been prepared. A rare example of a complex (46) containing -complexes. Key information is thus gained, not only on
a four-electron tridentate tin donor ligand was isolated,108 the structures and energetics but also on the dynamic pro-
and more recently, the complex Ru(SnPh3 )2 (P2 C2 Ph2 )2 with cesses that are common in these systems.105,112 RuH4 (PPh3 )3
two SnPh3 units and a bis(diphosphabutadiene) ligand was was mentioned as early as 1976 by Ashworth and Single-
reported.109 ton as possibly containing undissociated dihydrogen. This
was confirmed 10 years later by Crabtree and Hamilton who
reformulated it as RuH2 (H2 )(PPh3 )3 . Similarly, RuH6 (PCy3 )2
Ph2Sn OMe was reformulated as RuH2 (H2 )2 (PCy3 )2 (47), a rare example
CO
iPr P
Ph of a thermally stable bis-dihydrogen complex (see equa-
3 Ru Sn
L Ph tion 3). This complex displays a versatile reactivity, in some
Ph2Sn OMe cases, similar to RuH2 (H2 )(PPh3 )3 and RuH2 (N2 )(PPh3 )3 (see
Scheme 8). In particular, it reacts with halocarbons and thiols
(46)
to give the corresponding 16-electron dihydrogen complexes,
RuH(H2 )X(PCy3 )2 (X = Cl, I, SR). The chemistry of (47)
was reviewed in 1998 before the report of its X-ray crys-
tal structure in 2000.74,113 The reactivity of (47) with silanes
8 RUTHENIUM HYDRIDE COMPLEXES (See leading to the formation of new -silane complexes and to
Hydride Complexes of the Transition Metals and interesting catalytic applications has been briefly described
Dihydrogen Complexes & Related Sigma Complexes) in Section 7.103106 It was also possible to activate vari-
ous boranes, both stoichiometrically and catalytically (see
The rich chemistry of ruthenium hydride developed rapidly Boron Hydrides; Boron: Organoboranes, and Hydroboration
after the preparation of RuHCl(PPh3 )3 .1 The polyhydrides Catalysis).114,115 Remarkably, a complex incorporating two
RuH2 (PPh3 )4 and RuH4 (PPh3 )3 were synthesized by reduction boron-attached ligands coordinated with two different bonding
of RuCl2 (PPh3 )3 with hydride donor reagents such as modes, [RuH{(-H)2 Bpin}( -HBpin)(PCy3 )2 ], was isolated
NaBH4 . The dihydride RuH2 (PPh3 )4 can be used as an and proved to be an active species for catalytic formation of
interesting alternative to conventional Lewis acid and base vinyl boranes or for selective hydroboration of olefins.114 (47)
catalysts, as proven by its specific activity for nitrile is also a catalyst precursor for the hydrogenation of S-
activation.110 Numerous hydrido derivatives containing other and N-heteroaromatic substrates (see Hydrodesulfurization
anionic functional ligands were prepared, either by anionic & Hydrodenitrogenation).31,116 The presence of labile dihy-
substitution of chloride on RuHCl(PPh3 )3 or by reaction drogen ligands is the key factor in the ability of (47) to
of the polyhydrides with acidic compounds (equation 2). catalyze, at room temperature, the Murai reaction (CC
The synthesis of hydride complexes, using (BH4 ) or bond coupling of an olefin with a functionalized aromatic
(AlH4 ) , may involve the formation of Ru BH4 or compound. See CarbonCarbon & CarbonHeteroatom
Ru AlH4 derivatives with one or two bridging hydrides. Activation and Ruthenium: Organometallic Chemistry). In
The method of preparation by reduction of chloride the case of acetophenone, the resulting orthometalated com-
precursors has allowed the synthesis of derivatives of plex RuH(H2 )(o-C6 H4 C(O)Me)(PCy3 )2 displays remarkable
alkyl phosphines with a small cone angle, for example, spectroscopic properties as exchange couplings between the
RuH2 (PBu3 )4 . However, for bulky alkylphosphine derivatives, hydride and the coordinated dihydrogen molecule can be
the preparation involves hydrogenation of the ruthenium(0) detected by NMR.117
precursor Ru(C8 H10 )(C8 H12 ) (see equation 3).
RuH2 (L)(PPh3 )3 + HX RuHX(PPh3 )3 + L + H2 (2) PCy3

H
X = OCOR, SH, SR, Cl, etc; L = H2 , N2 , PPh3 H
H Ru
H2 , 2PCy3 H
Ru(C8 H10 )(C8 H12 ) RuH2 (H2 )2 (PCy3 )2 (3) H
H
PCy3
The discovery by Kubas of the coordination of dihydro-
(47)
gen without dissociation gave a new impetus to ruthenium
hydride chemistry (see Dihydrogen Complexes & Related
Sigma Complexes).111 As mentioned already in Section 7, Ruthenium polyhydride complexes containing monophos-
considerable progress in NMR and X-ray techniques have phaferrocenes are now available.118 In contrast to Cp ruthe-
allowed better characterization of many compounds and, nium chemistry, the use of a trispyrazolyborate ligand favors
in particular, better discrimination between a dihydride or the formation of dihydrogen structures: the chemistry of Tp
DOI: 10.1002/0470862106.ia208
Cy3P O acidic dihydrogen ruthenium complex as catalyst results in

heterolytic cleavage of H2 and, for example, in catalytic
O H O B hydrogenolysis of trimethylsilyl enol ethers.122 A review was
B Ru H published in 1998 on the properties of dihydrogen complexes
O H
as homogeneous reduction catalysts (see Hydrogenation &
H
PCy3 Isomerization of Alkenes).123 NMR methods play a major
role in the characterization of polyhydrides (JHD , T1 ; rate
2HBpin PCy3 of intramolecular exchange; rate of exchange with other
PCy3
X H
incoming ligands). The parahydrogen-induced polarization
L H N2 or CO RX or HSR Ru (PHIP) method is a relatively new NMR technique that can also
Ru (47) H
bring valuable information on the detection of intermediates.
L H
H It can be used as a mechanistic probe in highly fluxional
PCy3
PCy3 HSiR3
systems, as was illustrated in ruthenium hydride carbonyl
N YH X = Cl, I, SR systems.124
L = N2, CO
H PCy3
+ 2+
Cy3P H N H
H
Ru Ru H PR3
H SiR3 H Ph2 Ph2
Y P N CO
H H P
H Ru Ru H
PCy3 PCy3 N
P P
Ph2 Ph2
Y = O, NH, Ph H PR3 H
(48) (49)
Scheme 8
Unusual ruthenium porphyrin dihydrogen complexes were

and Bp ruthenium complexes has been briefly described in also obtained.111 Dinuclear hydride or dihydrogen complexes
Section 5.4.7479 generally result from the dimerization of hydride and/or
Anionic polyhydride derivatives were obtained by reaction chloride precursors. A number of bioctahedral complexes
of potassium naphthalenide with RuHCl(PPh3 )3 in THF. of central core Ru(-X)3 Ru have thus been prepared. The
Addition of H2 yields the trihydride [RuH3 (PPh3 )3 ] , properties of the dinuclear complex [RuHCl(Pi Pr3 )2 ]2 have
whereas the intermediacy of a diphenylbutadiene derivative is been extensively studied by Caultons group, and a rich
necessary to reach the pentahydride [RuH5 (PPh3 )2 ] after organometallic chemistry has been reported.125 Ruthenium
elimination of one phosphine ligand. A one-pot reaction hydride complexes have been used to prepare heterobimetallic
was obtained by using a mixture of RuCl3 /2.5 Pi Pr3 , KH, complexes. Three strategies have been employed: (1) use of
and a crown ether under a dihydrogen atmosphere. Interion a ruthenium anion and reaction with transition metal chloride
proton hydride NH HRu interactions exist in the salts derivative or vice versa, (2) addition of Lewis acidic cations
[K(Q)][RuH5 (Pi Pr3 )2 ] when Q is 1-aza-18-crown-6 or 1,10- to ruthenium hydrides, and (3) use of bridging ligands. The
diaza-18-crown-6.119 mixture of cis- and trans-RuH2 (dppm)2 is, for example, able
Cationic derivatives are prepared by protonation (which to react with a variety of metallic fragments to yield mono-
can lead to dihydrogen evolution) or by halide abstraction or bis-dppm-bridged hydrido species. An unusual example
in the presence of dihydrogen. The cations [RuH3 L4 ]+ and of a ruthenium iridium complex, a mixed hydrido-alkoxide
[RuH5 L3 ]+ can be prepared by one of these methods. Most bridge, was reported.126
of the [RuH3 L4 ]+ complexes have now been reformulated Hydrogen bonding is a well-known phenomenon that has
as [RuH(H2 )L4 ]+ . An important class of hydride derivatives led to major developments during the last decade in the field
contains chelating phosphorus-donor groups. Thus, the neutral of polyhydrides. The formation of the so-called dihydrogen
RuHX(L2 )2 (X = H, Cl; L2 = dppm, dppe, dcype, etc.) can bond (MH HX) can occur intermolecularly between a
adopt a cis or a trans configuration, but the corresponding hydride and a weak acid (see equation 4) or intramolecularly
cationic dihydrogen species ([RuX(H2 )(L2 )2 ]+ ) all display between a hydride and a pendant ligand with an NH or OH
a trans configuration. These compounds were extensively group. This type of interaction is very important as it may
studied, and [RuH(H2 )(dppe)2 ]+ (48) is one of the few control reactivity and selectivity in solution. A few examples
complexes characterized by a neutron diffraction structure.120 have appeared in ruthenium chemistry.127,128
Dicationic complexes, as shown in structure (49), can
+
also be prepared, and they display even more acidic H H
(4)
properties than many cationic complexes.121 The use of an Ru H +H X Ru H H X Ru X
DOI: 10.1002/0470862106.ia208
9 POLYNUCLEAR COMPLEXES OF RUTHENIUM 4. C.-M. Che and T.-C. Lau, in Comprehensive Coordi-
nation Chemistry II, eds. T. J. Meyer and J. A. McCleverty,
Pergamon Press, Oxford, 2003, Vol. 5, p. 733.
The chemistry of ruthenium carbonyl clusters is presented 5. K. Wohnrath, M. Peres de Araujo, L. R. Dinelli, A. A. Batista,
in Ruthenium: Organometallic Chemistry and Polynuclear I. de Sousa Moreira, E. E. Castellano, and J. Ellena, J. Chem.
Organometallic Cluster Complexes, so the subject of metal Soc., Dalton Trans., 2000, 3383.
particles deposited on supports will not be described in
6. W. J. Casteel Jr, D. H. Lohmann, and N. Bartlett, J. Fluorine
this article (see Ruthenium: Organometallic Chemistry and
Chem., 2001, 112, 165.
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concerning giant clusters and the molecular chemistry of
2003, 2184.
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the last decade. The ruthenium complex Ru(C8 H10 )(C8 H12 ), 8. C. Becker, I. Kieltsch, D. Broggini, and A. Mezzetti, Inorg.
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composed of a core of a few nanometers adopting the hcp Pereira, J. A. H. Da Jordana, and S. Hull, J. Phys. Chem.
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10 RELATED ARTICLES
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K. C. Lau, and W. K. Li, J. Am. Chem. Soc., 2000, 122, 11380.
Asymmetric Synthesis by Homogeneous Catalysis; Coor- 17. T. J. Meyer and M. H. V. Huynh, Inorg. Chem., 2003, 42,
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19. N. C. Zanetti, F. Spindler, J. Spencer, A. Togni, and G. Rihs,
Catalysis by Metals; Hydride Complexes of the Tran-
Organometallics, 1996, 15, 860.
sition Metals; Luminescence; Luminescence Behavior &
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Ruthenium: Inorganic & Coordination Chemistry: Sylviane Sabo-Etienne & Mary Grellier

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Ruthenium: Inorganic & However, its blue chloride solution had been previously

observed by Vauquelin in Paris in 1804. Ruthenium is the least

MeCO2H the mixture. We will, nevertheless, refer to the common

the fluoro ligand, terminal versus bridging, plays an important L

3.1 Ruthenium Homoleptic Oxo Species (3)

Ru(O2 CCF3 )2 (ROH)2 (PP), incorporating various chiral phos-

hydrido derivatives such as RuH(OH)(PPh3 )2 (H2 O).1,2 A Cl H 2N NH2 Cl

4.2 Thioethers and Analogous Derivatives

Supramolecular chemistry involving transition metal

by carboxylate groups (see Semiconductor Interfaces and

sensitive diagnostic agents. Metallointercalators contain O O O

reduction of coordinated nitric oxide. For example, Shepherd

PF3 has found wide use as a precursor for other ruthenium(II)

O OH (PP3 = P(CH2 CH2 PPh2 )3 ) was used as an entry to mono- and

6.3 Polydentate Phosphines, Pincer Ligands,

RuH2 (L)(PPh3 )3 + HX RuHX(PPh3 )3 + L + H2 (2) PCy3

Cy3P O acidic dihydrogen ruthenium complex as catalyst results in

Unusual ruthenium porphyrin dihydrogen complexes were

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