CH20147 Transition Metal Chemistry

Part 2 Dr. A D Burrows

The Se!tro!hemi!al Series
Strong fed gands, hgh
oct
, ow spn Weak ed gands, ow

oct
, hgh spn
-acceptors -donors -
donors
M" ener#y le$el %ia#ram &or 'M()*
n+
Orbtas nteract f they have the same symmetry
Add n eectrons from meta as approprate
Ony shows -bonds
-donor gands (e.g. hades, O
2-
) reduce
oct
- repusons between ed p
z
and d
xy
, d
xz
,
d
yz
-acceptor gands (e.g. CO, CN
-
, PPh
3
) ncrease
oct
- backbondng
-bondng nvoves gand donatng 2 eectrons to empty meta d orbta
back-bondng nvoves -eectron donaton from fed meta d-orbta to empty gand
-orbta
covaency - parng energy and ntereectronc repuson ess n compexes
due to "nepheauxetc (coud expandng) ehect" of gands
Metal Car,onyls
Backbondng strengthens M-C bond, but weakens C-O
Eectron densty goes nto antbondng orbta on CO - decreases bond order
Shown by decrease n stretchng frequency - weaker bond requres ess energy
Phoshines -P.
/
0
Lone par on P makes them good -donors
Aso -acceptors (not as good as CO), usng P-C -orbtas
Sterc ehects - Toman cone ange
Har% an% so&t a!i%s an% ,ases
Hard (hgh charge densty, non-poarsabe) catons stabe wth hard gands, and vce
versa.
1irst .ow Transition Metals
S!ary Tiger, 2ery Crazy, Man 1eeder, Cooked 3ine Cuddy 4ebras
1st row generay dherent from 2nd and 3rd rows

oct
a
1g
a
1g
*
e
g
e
g
*
t
2g
t
1u
t
1u
*
4s
4p
3d
M
n+
ML
6
n+
6 x L
1st row eectronc and magnetc propertes can be expaned by CFT
Wder range of coordnaton numbers for 2nd and 3rd row (usuay 4 or 6 for 1st)
Trends n oxdaton states dherent, but maxmum usuay same
More meta-meta bondng n 2nd and 3rd rows
"5i%ation states
For Sc Mn, max oxdn. state corresponds to remova of a 3d and 4s eectrons
Approxmatey mrror mage for Fe Cu
In compex, 4s eectrons are ost before 3d
Most common oxdn. state goes down from +3 to +2 across group
Resut of ncreasng 3rd onsaton energy across group (though dp from Mn to Fe)
Core-ke behavour of d orbtas ncreases across group
Stabty of certan oxdn. states strongy ahected by gands (e.g. hgher wth F
-
than
C
-
or Br
-
)
0 or negatve oxdn. states possbe wth -acceptor gands
Hgh oxdn. states possbe wth -donor gands
Hgh pH tends to favour hgh oxdn. state
S!an%ium (+3 mportant oxdaton state)
Sc
3+
ony mportant oxdn. state - coouress, strong Lews acd - chemstry smar to
aumnum
Titanium (+4, +3, +2)
+4 most mportant - coouress, strong Lews acd, exsts n souton as TO
3
2-
or TO
2+
T(IV) can be reduced, to T
3+
, a strong reducng agent.
No aqueous chemstry for T
2+
- reacts voenty wth water
2ana%ium (+5, +4, +3, +2)
Vanadum (V) reduced to VO
2+
(bue), V
3+
(green) and V
2+
(voet, strongy reducng)
Many VO
2+
compexes square pyramda, can coordnate extra gand at axa poston
(opposte O)
Chromium (+6, +3, +2)
Cr(VI) s powerfu oxdsng agent - Cr
2
O
7
2-
n acd, CrO
4
2-
n aka
Cr
3+
has hgh CFSE (-1.2
oct
), so s knetcay nert
Man#anese (+7, +3, +2)
Mn(VII) strong oxdsng agent, exsts as MnO
4
-
(tetrahedra) - coour due to LMCT
Mn(III) s d4, so experences |ahn-Teer dstortons
Mn(II) s very pae n coour, as a ts transtons are forbdden by a seecton rues
6ron (+3, +2)
Fe
3+
and Fe
2+
are ready nterconverted - stabty depends on gands
Fe
3+
s acdc n souton and w form |Fe(OH)
3
(OH
2
)
3
| precptate at pH > 2
Compounds wth both oxdn. states strongy cooured due to M M charge transfer
Co,alt (+3, +2)
Co(III) strong oxdsng agent, but ow spn knetcay nert (hgh CFSE)
Coour of Co(II) depends on geometry
3i!7el (+2)
N(II), d8, s generay stabe to oxdaton or reducton
Can have varous geometres - tetrahedra, sq. panar, trg. bpyramda, sq.
pyramda, octahedra
Coer (+2, +1)
Octahedra Cu(II) compexes (d9) experence |ahn-Teer dstortons - can ose axa
gands
4in! (+2)
Zn
2+
s coouress, wth a varety of geometres. Borderne transton meta
Chromium8 Moly,%enum an% Tun#sten
Cr(VI) strong oxdsng agent, W(VI) not ready reduced
Mo and W more ready adopt hgher oxdn. states and coordnaton numbers
3i!7el8 Palla%ium an% Platinum
Pd(II) and Pt(II) most commony adopt square panar
M-M bonds and ow oxdn. states (+1, 0) more mportant down group
Bioinor#ani! Chemistry
9 Transton metas (V, Cr, Mn, Fe, Co, N, Cu, Zn and Mo) are essenta for fe
Structura roes - stabsng proten structures
Functona roes - on nvoved n reactvty
"5y#en trans&er an% stora#e
Haemogobn (Hb) - transfers oxygen from ungs to tssues
Myogobn (Mb) - stores bood unt t s needed
Haem group = ron bound to a porphyrn rng
Hb = 4 haem groups, Mb = 1
Each haem group can absorb one moecue of O
2
, and they gve red coour to bood.
In deoxyhaemogobn, Fe(II) s square-pyramda (wth axa hstdne), 0.4A outsde
haem pane
O2 bonds to sxth ste, Fe becomes ow spn, so ant-bondng e
g
s empty and on s
smaer
The Fe s then abe to t nto the pane of the haem rng
O2 bonds reversby, so can drop oh (CO bonds rreversby, so t toxc)
Oxygen s formay superoxde, O
2
-
, and ron oxdsed to Fe(III)
Cooperatvty - when one O
2
bnds, amnty of other Fes for O
2
ncreases
Mb bnds to O
2
better at ow O
2
concentratons, so n tssue Hb reeases O
2
and Mb
takes t up
Low pH, Hb reeases O
2
better, metabosm gves CO
2
ower pH, hepng transfer of
O
2
n ces
Other compounds used n other organsms, e.g. haemocyann (mouscs/arthropods
bue bood)
9le!tron trans&er roteins
At mtochondra, boogca fues are turned nto energy
Eectron transfer takes pace through a number of steps, wth a sma change n
potenta at each
Meta centre provdes reversbe ste for eectron (e.g. ron - 2 ready avaabe oxdn.
states)
Ferrodoxns - ron-sufur protens, 2, 3 or 4 ron centres, eectrode potenta < 0V
Cytochromes - ron-haem protens, hgher eectrode potentas, 4 types:
o cytochrome a: haem group contans CHO group - 5- or 6-coordnate
o cytochrome b: proten not covaenty bonded to haem - 6 coordnate, ow spn
o cytochrome c: proten s covaenty bonded to haem - 6 coordnate, ow spn
o cytochrome d: haem s dhydroporphyrn
Cytochrome c oxdase - has 2 Fe and 2 Cu meta centres - transfers eectrons to O
2
Ferrtn - hoow proten wth cavty ed wth crystased ron compex to store ron
Cis:latin
Potent ant-tumour agent, cs-|PtC
2
(NH
3
)
2
|
Enough C n body to stay ke that unt reaches ces, then C substtuted for H
2
O
H
2
Os then repaced by Ns from neghbourng Gs on DNA, dsruptng hex, nhbtng
repcaton
However, ony works for sma range of tumours, has sde ehects, s nsoube n water,
and can ead to deveopment of resstance
Research contnues nto smar compounds wthout the probems
Thermo%ynami!s an% ;ineti!s
Thermodynamcs - extent of reacton - reates to G
0
, quanted by equbrum
constant, K
Knetcs - speed of reacton - reates to G

(actvaton energy), quanted by rate

constant, k
1ormation Constants
K decreases for successve substtutons of H2O by another gand
Decrease n number of water moecues avaabe - substtuton gets harder
Chelate e<e!t
Cheate gand = monodentate gand that forms a rng structure wth the meta centre
Compexes wth cheate gands more stabe than those wth monodentate gands
Due to entropy - monodentate gands cheatng gands brng ncrease n dsorder
(i#an% su,stitution rea!tions
ML
x
X + Y ML
x
Y + X
3 mechansms for substtuton (techncay a spectrum between the extremes):
a) Dssocatve (D) - 2 step process - X fas oh rst, and then Y repaces t
b) Assocatve (A) - 2 step process - Y adds on rst, then X fas oh
c) Interchange - 1 step - X ost and Y ganed smutaneousy, va transton state
S=uare lanar !omle5es
Normay undergo substtuton through assocatve mechansm
Most study has been done on Patnum, as t s:
Vrtuay aways square panar
Reatvey nert to oxdaton/reducton
Rate of gand substtuton sow, so reatvey easy to study
9$i%en!e &or Asso!iati$e Me!hanism
k's for dspacement of C
-
by H
2
0 (NH
2
??) smar - dssocatve woud depend on
charge
Reactons usuay occur wth stereoretenton at Pt
Large, negatve S

(entropy of actvaton), so transton state s more ordered

Increase n pressure gves ncrease rate and arge, negatve voume of actvaton (V

)
observed
;ineti!s o& Asso!iati$e .ea!tions
Mght expect reacton to be second order, but s more compex
In excess of |Y|, |Y| unchanged by reacton, gves pseudo-rst order condtons:
Rate = k
obs
|PtL
3
X| k
obs
= k
1
+ k
2
|Y|
Pot k
obs
aganst |Y| ntercept = k
1
, gradent = k
2
Intercept unchanged by enterng group, but ahected by sovent k
1
dependent on
sovent
k
1
mechansm s addton of sovent, oss of X, addton of Y, oss of sovent
6n>uen!e o& the enterin# #rou
For patnum, softer gands (e.g. PR3, CN-) gve hgher rate constant
See hard and soft acds and bases - soft prefer soft, hard prefer hard (patnum s soft)
6n>uen!e o& the se!tator li#an%s
Due to stercs, buky spectator gands sow down reacton (especay when cs to
eavng group)
Suggests process goes va trgona bpyramda ntermedate, not square pyramd
The trans e<e!t
Certan gands, when trans (T) to the eavng group (X), make the reacton more abe
a0 ?:e&&e!ts@
T and X compete for same meta orbtas n ground state (ess competton n
transton state)
Therefore strong -donors (e.g. H-, PMe
3
) destabse ground state, owerng actvaton
energy
,0 A:e&&e!ts
If T s a good -acceptor, t accepts charge from the ncomng gand
Ths owers the energy of the transton state, and so agan owers the actvaton
energy
The trans in>uen!e
Ehect of gand on ground state propertes, e.g. bond engths, NMR coupng constants
-effects not mportant, as transton state not nvoved, so -acceptors ower down
seres
Su,stitution in "!tahe%ral !omle5es
Commony studed usng Cr
3+
(d
3
) and Co
3+
(d
6
), as compexes are nert due to CFAE
Study water exchange and anaton (substtuton of water for X
-
)
Undergo substtuton through dssocatve mechansm
Rate ahected by:
Charge - hgher charge ess abe (sower exchangng) gands
CFAE - dherence between oct. CFSE and sq. pyramda CFSE - hgh CFAE sow
reacton
9$i%en!e &or Disso!iati$e me!hanism
Rates generay unahected by enterng group
Rates depend on nature of eavng group (proportona to M-X bond strength)
Rates ncreased by ncreased buk of spectator gands
Pressure ncrease gves rate decrease (postve V

)
A!i% an% Base Catalysis
Acd catayss - eavng group protonated f t has avaabe one par
Base catayss - e.g. deprotonates NH
3
, eavng group then substtuted for OH
-
9le!tron Trans&er Pro!esses
Redox reactons nvove transfer of eectrons; two types - nner sphere and outer
sphere
"uter Shere 9le!tron Trans&er
Reactants wth dherent bond engths - vbratons equase bond engths transfer
can occur
Greater change n bond engths requred sower reacton
6nner Shere 9le!tron Trans&er
Invoves covaenty bonded brdgng gand - maybe but not necessary transferred
wth eectron
e.g. Co
3+
(nert) + Cr
2+
Co
2+
+ Cr
3+
(nert) - C
-
transferred wth eectron
Co
3+
coudnt ose C
-
, Cr
3+
coudnt gan t, as both are nert, so must be bonded to
both n ntermedate