Tema X

Formulacin y
nomenclatura de compuestos de coordinacin
Seminario 1
Nomenclature of Inorganic Chemistry.
IUPAC Recommendations 2005
Edited by N. G. Connelly, T. Damhus, R. M. Hartshorn and A. T. Hutton.
The Royal Society of Chemistry, 2005
!
Formulacin
Las entidades de coordinacin se escriben entre corchetes independientemente de su carga.
[Ni(CN)
4
]
2-
[Fe(CO)
5
] [Cr(NH
3
)
6
]
3+

En primer lugar se escribe el smbolo qumico del tomo central, despus los ligandos
ordenados por orden alfabtico de los primeros smbolos de sus frmulas, abreviaturas o
acrnimos.
Un smbolo de una letra siempre precede a un smbolo de dos letras. Si los primeros
smbolos son iguales se coloca en primer lugar el que tiene un subndice menor. Si esto no
fuera suciente se utilizan los smbolos posteriores.
Cl
-
y CO CO precede a Cl
-

H
2
O y NH
3
H
2
O precede a NH
3
(H antes que N)
OH
2
y NH
3
NH
3
precede a OH
2
(N antes que O)
NO
2
-
y NO
3
-
NO
2
-
precede a NO
3
-

NH
3
y MeCN NH
3
precede a MeCN
Cuando los ligandos son poliatmicos sus frmulas se encierran entre parntesis. Lo mismo
es aplicable a las abreviaturas de los ligandos. Los signos de insercin se ordenan dentro de
los corchetes de la siguiente manera: [{()}]. Por ejemplo, [PtCl
2
{P(C
6
H
5
)
3
}
2
].

#
Los iones complejos pueden formar parte de sales complejas y ese caso el catin siempre
precede al anin:
K
2
[Fe(CO)
4
] Na[PtBrCl(NH
3
)(NO
2
)]
[Co(N
3
)(NH
3
)
5
]SO
4
[Cr(NH
3
)
6
]Cl
3
Nomenclatura
1.- En primer lugar se nombran los ligandos en orden alfabtico, sin tener en cuenta los
prejos multiplicadores que indican el nmero de ligandos, despus se nombra el tomo
central indicando su nmero de oxidacin con nmeros romanos entre parntesis.
2.- Si la entidad de coordinacin es neutra o catinica el tomo central no cambia de nombre.
Sin embargo, en las entidades de coordinacin aninicas el nombre del metal se termina en -
ato (aluminato, cromato, cobaltato, niquelato, cuprato, aurato, ferrato, argentato,
estannato....).
3.- El nmero de ligandos de cada tipo se indica mediante los prejos:
di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca-, dodeca-
Los prejos bis-, tris-, tetrakis-, pentakis-, etc. se utilizan para evitar ambigedades. En este
caso hay que poner siempre el nombre del ligando entre parntesis: bis(metilamina) vs.
dimetilamina.

$
4.- Los nombres de los ligandos aninicos, tanto inorgnicos como orgnicos, se modican
para terminar en o. En general, si el nombre del anin termina en o se mantiene el mismo
nombre. As, los ligandos halogenuro, X
-
, se denominan: uoruro, cloruro, bromuro y yoduro.
Del mismo modo, los miones CN
-
y SCN
-
se denominan cianuro y tiocianato,
respectivamente. El hidrgeno en los complejos, excepto en los complejos con hidrgeno
molecular, se considera un ligando aninico y se denomina hidruro.
5.- Los nombres de los ligandos neutros y catinicos, incluidos los ligandos orgnicos, se
usan sin modificaciones.
Algunos ejemplos:
[Ni(CN)
4
]
2-
ion tetracianuroniquelato(II)
[Fe(CO)
5
] pentacarbonilhierro(0)
[Cr(NH
3
)
6
]
3+
ion hexaamminocromo(III)
Las sales que contienen iones complejos se nombran de la siguiente manera:
[Cr(NH
3
)
6
]Cl
3
cloruro de hexaamminocromo(III)
K
4
[Fe(CN)
6
] hexacianuroferrato(II) de potasio

%
"#

tomo central: el tomo A antes mencionado (B, Pt, Fe...)
Ligando: cada uno de los tomos (B) o grupos de tomos (C) unidos al
tomo central (Cl
-
, F
-
, NH
3
). Suelen ser neutros aninicos. El ligando se une
al tomo central a travs del tomo de coordinacin (Cl, F, N).
La frmula de la entidad de coordinacin se suelen encerrar entre corchetes. El
orden en que se escriben los componentes del complejo es: [tomo central +
ligandos inicos + ligandos neutros]
Dentro de cada grupo de ligandos, stos se colocan en orden alfabtico del
smbolo del tomo de coordinacin.
Ejemplos: [CoCl
2
(NH
3
)
4
]Cl; [Al(OH)(H
2
O)
5
]
2+

NOMBRES DE LIGANDOS
Ligandos aninicos:
Terminan en -o. Se nombran como si fueran aniones, con algunas
excepciones.
Ejemplos:
F
-
fluoruro (fluoro) Cl
-
cloruro (cloro)
Br
-
bromuro (bromo) I
-
yoduro (yodo)
OH
-
hidrxido (hidroxo) O
2-
xido (oxo)
O
2
2-
perxido (peroxo) H
-
hidruro
HO
2
-
hidrgenoperoxido CN
-
cianuro (ciano)
SCN
-
tiocianato PO
4
3-
fosfato
NO
3
-
nitrato NO
2
-
nitrito
S
2-
sulfuro (tio) HS
-
hidrgenosulfuro, sulfanuro
(mercapto)
Entre parntesis se ha escrito el nombre obsoleto de esos ligandos porque es
frecuente encontrarlo todava en la bibliografa.

Los radicales hidrocarbonados se nombran como tales en compuestos de
coordinacin.
Radical Nombre Carga Radical Nombre Carga
CH
3
Metil -1 C
2
H
5
Etil -1
&
!"#$% ''

'eta-! was originally developed to indicate how many
carbons oI a -system were coordinated to a metal center.
Hapticity is another word used to describe the bonding mode
oI a ligand to a metal center. You will occasionally see h
!
used instead
oI
!
, although this usually an error caused by Iorgetting to turn a
regular Iont h into the !"#$%& Iont on most word processors in order to
get a Greek . An
5
-cyclopentadienyl ligand, Ior example, has all Iive
carbons oI the ring bonding to the transition metal center.

'
values for carbon ligands where the x value is odd usually
indicate ()*%)*+ carbon ligands (e.g.,
5
-Cp,
1
-CH
3
,
1
-allyl or
3
-
allyl,
1
-CHCH
2
). The # of electrons donated (ionic method of
electron counting) by the ligand is usually equal to ' + 1. Even
'

values usually indicate ),-./(& carbon -system ligands (e.g.,
6
-
C
6
H
6
,
2
-CH
2
CH
2
,
4
-butadiene,
4
-cyclooctadiene). The # of
electrons donated by the ligand in the even (),-./(&) case is usually
just equal to '.

(

(

(


(

5
-Cp
3
-Cp
3
-allyl
1
-allyl

The nomenclature, however, has been generalized by most in the
organometallic Iield to include non-carbon ligands when there is some
question as to the bonding mode (or hapticity) oI the ligand donor atoms
to the metal. For example, the bisphosphine Ph
2
PCH
2
CH
2
PPh
2
(dppe)
is normally a chelating ligand, but there are metal complexes known
where only one oI the phosphine atoms is coordinated to the metal
center and the other is 'dangling.

!

!"#$% ''

'eta-! was originally developed to indicate how many
carbons oI a -system were coordinated to a metal center.
Hapticity is another word used to describe the bonding mode
oI a ligand to a metal center. You will occasionally see h
!
used instead
oI
!
, although this usually an error caused by Iorgetting to turn a
regular Iont h into the !"#$%& Iont on most word processors in order to
get a Greek . An
5
-cyclopentadienyl ligand, Ior example, has all Iive
carbons oI the ring bonding to the transition metal center.

'
values for carbon ligands where the x value is odd usually
indicate ()*%)*+ carbon ligands (e.g.,
5
-Cp,
1
-CH
3
,
1
-allyl or
3
-
allyl,
1
-CHCH
2
). The # of electrons donated (ionic method of
electron counting) by the ligand is usually equal to ' + 1. Even
'

values usually indicate ),-./(& carbon -system ligands (e.g.,
6
-
C
6
H
6
,
2
-CH
2
CH
2
,
4
-butadiene,
4
-cyclooctadiene). The # of
electrons donated by the ligand in the even (),-./(&) case is usually
just equal to '.

(

(

(


(

5
-Cp
3
-Cp
3
-allyl
1
-allyl

The nomenclature, however, has been generalized by most in the
organometallic Iield to include non-carbon ligands when there is some
question as to the bonding mode (or hapticity) oI the ligand donor atoms
to the metal. For example, the bisphosphine Ph
2
PCH
2
CH
2
PPh
2
(dppe)
is normally a chelating ligand, but there are metal complexes known
where only one oI the phosphine atoms is coordinated to the metal
center and the other is 'dangling.

!

!"#$% ''

'eta-! was originally developed to indicate how many
carbons oI a -system were coordinated to a metal center.
Hapticity is another word used to describe the bonding mode
oI a ligand to a metal center. You will occasionally see h
!
used instead
oI
!
, although this usually an error caused by Iorgetting to turn a
regular Iont h into the !"#$%& Iont on most word processors in order to
get a Greek . An
5
-cyclopentadienyl ligand, Ior example, has all Iive
carbons oI the ring bonding to the transition metal center.

'
values for carbon ligands where the x value is odd usually
indicate ()*%)*+ carbon ligands (e.g.,
5
-Cp,
1
-CH
3
,
1
-allyl or
3
-
allyl,
1
-CHCH
2
). The # of electrons donated (ionic method of
electron counting) by the ligand is usually equal to ' + 1. Even
'

values usually indicate ),-./(& carbon -system ligands (e.g.,
6
-
C
6
H
6
,
2
-CH
2
CH
2
,
4
-butadiene,
4
-cyclooctadiene). The # of
electrons donated by the ligand in the even (),-./(&) case is usually
just equal to '.

(

(

(


(

5
-Cp
3
-Cp
3
-allyl
1
-allyl

The nomenclature, however, has been generalized by most in the
organometallic Iield to include non-carbon ligands when there is some
question as to the bonding mode (or hapticity) oI the ligand donor atoms
to the metal. For example, the bisphosphine Ph
2
PCH
2
CH
2
PPh
2
(dppe)
is normally a chelating ligand, but there are metal complexes known
where only one oI the phosphine atoms is coordinated to the metal
center and the other is 'dangling.

!

Intro 12
M PPh
2
PPh
2

1
-dppe
The nomenclature Ior such a singly coordinated bisphosphine ligand
would be: M(
1
-dppe) -- meaning that only one oI
the two possible phosphorus atoms is bonded to
the metal. Note that in cases like this, having an
odd hapticity does NOT mean that the ligand is
anionic (it is, however, a 2 electron donor!). When
dppe is coordinated in it`s normal chelating mode, one usually omits the

2
-designation, as this is considered redundant. Note that some authors
use
!
instead oI
!
when reIerring to non-carbon ligands.

'mu-! is the nomenclature used to indicate the presence oI a
!"#$%#&% (#%)&$ between two or more metal centers. The !
reIers to the number oI metal centers being bridged by the
ligand. Usually most authors omit ! 2 and just use to indicate that
the ligand is bridging the simplest case oI two metals.
*"$+"#&% There is no set method oI naming or ordering the listing
oI metal and ligands in a metal/ligand complex that most authors Iollow.
There are IUPAC Iormalisms, but hardly anyone Iollows them. There
are some qualitative rules that most authors seem to use in American
Chemical Society (ACS) publications:
1) in Iormulas with Cp (cyclopentadienyl) ligands, the Cp usually
comes Iirst, Iollowed by the metal center: Cp
2
TiCl
2

2) other anionic multi-electron donating ligands are also oIten listed in
Iront oI the metal.
3) in Iormulas with hydride ligands, the hydride is sometimes listed
Iirst. Rules # 1 & 2, however, take precedence over this rule:
HRh(CO)(PPh
3
)
2
and Cp
2
TiH
2

4) bridging ligands are usually placed next to the metals in question,
then Iollowed by the other ligands (note that rules 1 & 2 take
precedence): Co
2
(-CO)
2
(CO)
6
, Rh
2
(-Cl)
2
(CO)
4
, Cp
2
Fe
2
(-
CO)
2
(CO)
2

!

'
!
Se utiliza la convencin kappa para designar el modo de coordinacin
de ligandos ambidentados y polidentados.
trans-[Co(NO
2
)
2
(NH
3
)
4
]

cis-[Co(NH
3
)
4
(ONO)
2
]
2+
nitro-!#

nitrito-!O
[Cr
2
("-OAc)
4
(H
2
O)
2
]
tetrakis(-acetato-!O:!O')bisacuacromo(II)
(
Intro 12
M PPh
2
PPh
2

1
-dppe
The nomenclature Ior such a singly coordinated bisphosphine ligand
would be: M(
1
-dppe) -- meaning that only one oI
the two possible phosphorus atoms is bonded to
the metal. Note that in cases like this, having an
odd hapticity does NOT mean that the ligand is
anionic (it is, however, a 2 electron donor!). When
dppe is coordinated in it`s normal chelating mode, one usually omits the

2
-designation, as this is considered redundant. Note that some authors
use
!
instead oI
!
when reIerring to non-carbon ligands.

'mu-! is the nomenclature used to indicate the presence oI a
!"#$%#&% (#%)&$ between two or more metal centers. The !
reIers to the number oI metal centers being bridged by the
ligand. Usually most authors omit ! 2 and just use to indicate that
the ligand is bridging the simplest case oI two metals.
*"$+"#&% There is no set method oI naming or ordering the listing
oI metal and ligands in a metal/ligand complex that most authors Iollow.
There are IUPAC Iormalisms, but hardly anyone Iollows them. There
are some qualitative rules that most authors seem to use in American
Chemical Society (ACS) publications:
1) in Iormulas with Cp (cyclopentadienyl) ligands, the Cp usually
comes Iirst, Iollowed by the metal center: Cp
2
TiCl
2

2) other anionic multi-electron donating ligands are also oIten listed in
Iront oI the metal.
3) in Iormulas with hydride ligands, the hydride is sometimes listed
Iirst. Rules # 1 & 2, however, take precedence over this rule:
HRh(CO)(PPh
3
)
2
and Cp
2
TiH
2

4) bridging ligands are usually placed next to the metals in question,
then Iollowed by the other ligands (note that rules 1 & 2 take
precedence): Co
2
(-CO)
2
(CO)
6
, Rh
2
(-Cl)
2
(CO)
4
, Cp
2
Fe
2
(-
CO)
2
(CO)
2

!

)
[Co(H
2
O)
6
]
2+
ion hexacuacobalto(II)
[Fe(EDTA)]
2-
ion (etilenodiaminotetraacetato)ferrato(II)
[Fe(ox)
3
]
3-
ion tris(oxalato)ferrato(III)
K
3
[Fe(SCN)
6
]
hexatiocianatoferrato(III) de potasio
K[PtCl
3
(etileno)]
tris(cloro)etilenoplatinato(II) de
potasio
Formulacin
[Fe(en)
3
]
3+
ion tris(etilenodiamina)hierro(III)
K[PtCl
3
(etileno)] [Fe(ox)
3
]
3-
K
3
[Fe(SCN)
6
] [Fe(en)
3
]
3+
*
ion triamminobromuroplatino(II) ion tris(fenantrolina)rutenio(II)
ion hexahidroxidoestannato(IV) ion pentaacuahidroxidohierro(III)
!+
[Rh(CO)
2
I
2
]
-
[PtCl
2
(en)]
ion pentaacuabromurocromo(III) dicarbonilmetiltrisyodorodio(III)
!!
[IrCl(CO)(O
2
)(PPh
3
)
2
]
carbonilclorodioxgenobis(trifenilfosna)
iridio(I)
[Mn
2
(CO)
10
]
decacarbonildimanganeso(0)
[Fe(!
5
-C
5
H
5
)
2
bis(ciclopentadienil)hierro(II)
[Cr
2
(-OAc)
4
(H
2
O)
2
]
tetrakis(-acetato-kO:kO')bisacua
cromo(II)
[Re
2
Cl
8
]
2-
ion octaclorodirrenato(III)
[ReH
9
]
2-
ion nonahidrurorrenato(VII)
[IrCl(CO)(O
2
)(PPh
3
)
2
] [Re
2
Cl
8
]
2-
decacarbonildimanganeso(0)
!#
bis(-cloro)tetrakis(trimetilfosna)dirodio(I)
[Fe(#
5
-C
5
H
5
)
2
] [CoCl(NH
3
)
5
]
2+
ion tetraamminocloruro(dixidodeazufre)rutenio(II) ion nonahidrurorrenato(VII)
!$
ion pentaamminonitrocobalto(III) diammino(oxalato)platino(II)
[Ir(CO)Cl(PMe
3
)
2
] [Ru(NH
3
)
5
(N
2
)]
2+
!%