Organogold Chemistry:

I Structure and Synthesis

R V Parish
Department a/Chemistry, UMIST, Manchester, M60 1QD, UK

Organogold chemistry is enjoying a resurgence of interest as useful applications, largely physical or

medicinal, are being found. There is also a wide range of novel molecules, some with curious structures. This
article reviews the structures and syntheses of recently discovered gold compounds. A later article will
describe their reactions and applications.

Organogold derivatives have been known for almost example, reference 2), and deals with the preparation,
100 years. Many fascinating compounds and reactions structures, properties and applications of some of the
have been discovered but, until recently, they have more interesting organogold systems; the examples
found little practical application. However, the last ten given are drawn principally from those reported during
to fifteen years have seen the development of new the last ten years (a more comprehensive treatment is
materials with potential applications in non-linear found in reference 3). The intention is to exemplify
optics, conjugated linear polymers (potential molecular rather than to be comprehensive, and no mention at all
wires), liquid crystals, chemical vapour deposition and is made of cluster compounds. Complexes in which
anti-tumour agents (see Box 1). On the other hand, in carbonyl, cyano, or isonitrile ligands provide the only
marked contrast to the neighbouring noble metals, Au-C bonds are also ignored. For convenience, the
compounds of gold have been very little used in review is divided into two parts: this part deals with
homogeneous catalysis (but see reference 1). This the wide variety of organic ligands now available and
review attempts to update previous treatments (see, for the structure and synthesis of the gold compounds
derived from them; the second part treats the reactions
R-Au-PPhzo. R3P-Au -C:C-Au- PR3
and applications of these compounds.
luminescence R_Au-PPh{CH 2

COMPOUNDS AND STRUCTURES

Rod Polymers

Organic derivatives of gold are known for both of the

common oxidation states, +1 and +3, and there is an
Liqu id Cry stals Ro-Q-3- o - Q - C:C-AU-C:N-R increasing number of gold(II) derivatives. The normal
and predominant coordination numbers of gold are
~H3
two for gold(I) and four for gold(III); as is common in
MOCVD X3C-Au-PMaJ H3C- f u- PMC3 this part of the Periodic Table, this gives stable
CH3
(X p H. F) configurations with 14 and 16 electrons respectively.
Homoleptic compounds AuR or AuR 3 are
NM82

Anti tumour 6'I

-
~ L-x
I
X
(X ~ CI,OAc)
therefore electron deficient and are unstable and highly
reactive. This is true even though they achieve the
'normal' coordination number through polymerization
via bridging alkyl or aryl groups and three-centre two-
Box 1 Potential applicationsfor gold compounds electron bonds (see below). The principal examples of

CS9' GoldBulletin 1997,30(1) 3

 Gold(l) Gold(lll)

AuR(L) AuR 3L

AuR(X)- AuR 3X-

Box 2 Thepossible stoichiometries (L = neutralligand; X = anionic ligand; R = organic group)

stable compounds of empirical formula AuR are those

in which the R-groups carry a functionality which
allows polymerization by coordination to neighbouring Ketonyl
gold atoms (eg [AuC=CRJn)' Compounds formulated
originally as 'AuR3' or 'AuR3 ( O Et2) , are probably
Li[AuR 3BrJ (eg R = CH 3, C 6Fs) (4).
Provided additional ligands are present to make up
the coordination number, compounds of all possible Cerbene
stoichiometries are known, with one or two R-groups
bonded to gold(I) and from one to four to gold(III)
(Box 2). The structures of these compounds are as R'
expected, linear and square planar; where appropriate, Yllde Cl-lu -cH, -PR 3
geometrical isomers can usually be obtained. In effect, I
R'
the R-groups are carbanions acting as conventional,
mononegative, two-electron ligands. Being amongst
the softest ligands known", they transfer much electron Ylidelo
density to the gold atom; this is demonstrated, for
instance, by Mossbauer spectroscopic data (5, 6), and
they exert a high trans-influence. Compounds in which
Ph, Ph,
two R-groups are mutually trans are therefore generally P-Au-P
Ii ',:-,.
of lower stability, and other soft ligands usually adopt
positions cis to the R-group. For the same reason,
Ylldic
".
He;; : CH
P-Au-P../
Ph, Ph,
[AuR2r and [AultIr are highly reactive. In all cases,
derivatives of the harder perfluoro-organic groups -CF 3
and -C6FS show considerably greater stability. Ph, Ph,
H...... "P-Au-P"
1
AuL
2+
Melhanlde .....C, ...C......
lAu P-Au-P H

P
Ph, Ph,

HC=N
Box 3 Goldcompounds with less conventional ligandsystems
~ L,
\d,
CI

.o:;:..
I h
I

PPh 2
'" Au. . Br
'Br
II * The 'hardness' and 'softness' of metal ions and ligands correlates with their
polarizabiliry: metal ions which are small and highly charged, and ligands
which are small and electronegative, are 'hard', Large polarizable metal ions
or ligand donor atoms are 'soft', The trans-influence is the influence that a
ligand has on the strength of the metal-ligand bond trans to itself and
increases with the softness of the influencing ligand. The sequence of
Br
increasing softness of some common ligands is: Cl" < Br" < RS- < RJP <
III N ylide < /u'- < R-.

4 @ GoldBulletin 1997,30(1)
 LAu SiMea AuL ~
:"
~ "C,
/ LAU·~.· L.. SiMeal'
LAu SiMea ····. I ' SiMea
AuL
v VI AuL

Ph 2 Ph 2 /:·. . I· ~· · · · · ..
P-Au-P C -.
;:
HC:
'.\-
:CH
'~ ,\~ AU L
LA u ·.... . .'
\. ./ "' AuL
P-Au-P
Ph 2 Ph2
~ fH a
VII VIII
rr-Bonded organic ligands can be of all common
LAtI'
: \">LAU
.Y .:
LAu......· LAu
I
l+-
LA
.
Y
,"
tI\.">LAu
.
..
LAu..··..· LAu
r
types: alkyl, aryl, vinylic, acetylenic. The aryl
derivatives in particular lend themselves to the
formation of chelates when suitable substituents are
present; naturally, the stereochemistry required means · · tA.·:~.~AUJ+
...'
that these are limited to gold(III); examples are shown LAU:-:-::' ~::.:.
...... ... '> AuL
as I-N (7-10). . :.
Considerable attention has also been given to the AuL
synthesis of derivatives containing less conventional
ketonyl, diketonyl, carbene, or ylide ligands; examples Box 5 Examples ofcarbon-centred and hypervalent gold
are given in Box 3 (typical references: 11-19). The compounds
distinction between the different types is not always
obvious, and more than one can occur in the same contain gold-carbon bonds. It can, however, use the
molecule. A carbene may be considered, formally at residual electron density on the bridging carbon atom
least, as a neutral divalent carbon ligand, :CY2> where to bind extra gold atoms (VIII); to distinguish
Y is often an alkoxy or amido group. The most complexes of this type from conventional rr-bonded
common ylide ligands are effectively deprotonated organogold compounds, they are often called
phosphonium cations, eg :CH 2PPh3 (derived methanide complexes. Despite the unconventionality
from the methyltriphenylphosphonium cation, of some of these organic ligands, and the curiosity and
CH 3Ph3P+), therefore also neutral. The complexity of some of the structures (Box 4, references
dimethyldiphenylphosphonium cation can undergo 20-23), the stereochemistry at gold is highly normal.
two deprotonation stages to give :CH 2PPh2CH 2 - , The cyclic digold(l) ylide complexes are readily
which can act simultaneously as a conventional c- oxidized to give gold(III) complexes with conventional
bonded ligand and as an ylide; however, the negative square planar AUC 2X2 coordination but retaining the
charge is delocalized, and this ligand forms ring structure, VI, IX (24). With a single molar
symmetrical bridges: two such ligands bind to two gold equivalent of halogen, gold(II) derivatives (eg X) are
atoms forming an eight-membered ring system (V; obtained (25-26). Although the gold atoms now
VI). The dppm ligand, Ph 2PCH 2PPh2 , forms a similar formally have a d 9 configuration, the complexes are all
cyclic bis-gold(I) complex which can be deprotonated diamagnetic; the coordination is square planar and
to give VII. Although ylidic, this complex does not includes a short bond to the second gold atom. This

Box 4 Some 'exotic'ylidic and methanidicstructures

~ Gold Bulletin 1997, 30(1) 5

 .....-~ .
..
",: ,
- -,:
....
.. .
- ',. ......- ==<,. \ ":' .- ~~... ".
.- -
.- 2p - ":':::'" \:/..==.
'\". ..'- .. ./../ .. -

·\: : ~::i?\- \;:\~.,

.'

.\:.\~/ .......
"
Au
..........-
..•~ ..
C ..
' -- ..
"
. .
.....:-

ICAuL)e) 2+

Figure 1 MO schemes

behaviour is, of course, analogous to the long-

established mercury(I) compounds.
F3C<,
..... CH2
~Au--=--".
R2P, Br ..... Br PR2
"--Au:......-J
Bf
IX x
In recent years a series of compounds has been
discovered in which carbon atoms are a-bonded to one Figure 2 The molecular structure of[AuC= CBu'}1l (Reprinted
to six Au'L units, where L is a tertiary phosphine (Box with permission from reference 37).
5 - references 27-31). In those involving four-
coordinate carbon, the structures are basically experience an increase of mass. This affects their
tetrahedral but the Au-C-Au angles are often smaller energies and, for the valence shell, allows much more
than the tetrahedral angle rather than larger as might orbital mixing than would otherwise be expected. These
have been expected on steric grounds. Even more effects operate for all heavy atoms, but just happen to
curiously, the coordination number of the carbon atom have a maximum at gold.
increases readily above four, to five and even six; Other electron-deficient gold(I) compounds are
C(AuL)4 can be obtained only when L is a bulky best exemplified by AU2Zn2Ph6, for which structure XI
ligand, such as P(C6H Il h It should also be mentioned has been proposed (34). This type of bridging has been
that analogous 'hypervalent' compounds are known confirmed in the ferrocene derivative XII,
with central atoms other than carbon (eg boron, (CsHs)Fe[CsH4(AuPPh3h]+ (35). The well-established
oxygen, nitrogen, phosphorus, arsenic). (36) gold(I) alkynyl, [Au(C=CBut)]n' was for a long
Satisfactory molecular orbital schemes may be
constructed, in which the available valence electrons
just fill the bonding molecular orbitals (Figure 1). The
driving force for the formation of these remarkable
compounds is the tendency for gold atoms to attract
each other and for weak Au ...Au bonding interactions
to stabilize the compounds. Such interactions appear in
a wide range of compounds (32, 33), and are estimated
to have a strength comparable to hydrogen-bonds, ca
30 k] mol", This effect has been named 'aurophilicity'
(31), and is thought to be due to relativistic effects
arising from the high nuclear charge (33 and references
therein). Under its influence, electrons are accelerated
to velocities comparable to that of light and they XI XII

6 ~ Gold Bulletin 1997, 30(1)

 SYNTHESIS
The most versatile and most often used method for the
preparation of organogold compounds is the trans-
metallation reaction (2). Organolithium or Grignard
reagents readily replace halide bound to gold. For
gold(I), it is necessary to start with a complexed halide,
AuX(L) (Equation 1), and to avoid an excess of the
XIII XIV organometallic reagent unless it is intended to obtain
pO
-/t- C=C- CsH
CsFs S L-Au-X
RMgX
L-Au-R (1)
CsFs I
t u

PPh a L-Au-R
LiR

XV
the di-organoaurate(I) ion (Equation 2). Satisfactory
time assumed to have a tetrameric square structure (n = Grignard reagents can be made from fluoro-aryls, but
4), which would allow the triple bond to occupy the trilluoromerhyl derivatives are best formed from
second coordination site at an adjacent gold atom, and Cd(CF 3)z (42). With gold(III) halides, the diorgano
thus remove the electron deficiency. This material has derivative AuR2X is the usual first product when
recently been crystallized and found (37) to have a starting from AU2X6 or H[AuX.;]. Again further
much more fascinating, complicated structure involving reaction occurs readily with lithium reagents, to give
all possible bonding situations: one gold atom has two [AuR3X]- or [Au~L this is also a convenient way of
o-bonded alkynyl groups, one is 'IT-bonded to two making mixed organic-ligand derivatives, which do not
triple bonds, and a third has one (J- and one 'IT- bond. appear to undergo disproportionarion. Mono-
Two of each of these units are bound together in a ring organogold(III) derivatives are usually obtained from
in which the gold atoms form a flat regular hexagon, organomercury reagents, and this is most commonly
and two rings are interlaced (see Figure 2). A similar done with potential chelate ligands such as azo-
mix of (J- and 'IT-bonded groups may occur in the benzene or dimethylaminobenzylamine, eg to obtain I
gold(I) derivative of a propargyl-substituted calixarene, or IV (7,43,44).
XIII, (38) and is also seen in XIV and XV (39, 40).
Apart from the polymeric alkynyl derivatives, there is (N Q[AuCl41 r1
little evidence for 'IT-bonded complexes. The highly C-Hg-CI C-Au-CI (3)
unstable (explosive) cyclopentadienyl [Au(C5H5)].,
-QdHg 2Cl 61 I
CI
could polymerize either via three-centre bonds or by 'IT-
bonding analogous to that of the alkynyls, but nothing
is known of its structure. In the substituted monomeric ~
C-Hg-CI
(!ht)AuC1 3 r1
C-Au-CI (4)
derivatives, such as Ph3PAu(C5H5) , the -HgClz, tht I
cyclopentadienyl group is expected to be bound as a (J- CI
bonded monohapto ligand (Tjl, two-electron donor). In the normal solvents (acetone or acetonitrile), the
However, these molecules are fluxional on the NMR reactions represented by Equations 3 and 4 (Q = Na or
timescale and all carbon atoms are equivalent; as in Me4N; tht = rerrahydrorhiophene) are generally more
other cases, the 1,2-shift may involve transient 'IT- efficient, but they appear to be finely balanced
bonded intermediates (41). equilibria; it is sometimes necessary to add Me4N Cl to
encourage the precipitation of (Me4N)z[Hg2CI6] (43).
For some ligands (eg as in XVI, XVII) even this is not
effective, but reaction will proceed if a more polar
solvent is chosen, such as DMSO (10). It has been
postulated that these reactions proceed via a bridged
intermediate, XVIII, and that the solvent may inhibit
the coordination of the N-donor group to the mercury
atom and allow it to bind to the gold (10). This is

(69' GoldBulletin 1997, 30(1) 7

 0 was found that some of these adducts will undergo an

CST
0 ... 11 ortho-metallation reaction, such as the transformation
"'S- NMe2
of:XX into XXI (46). This is effected by refluxing the
I
b-
~ !J A1U-CI
CI
~ !J Ai- C'
CI
adduct in aqueous acetonitrile (3: 1), and similar
reactions have been used recently to prepare a range of
C,N-bonded gold (III) chelates containing six-
XVI XVII membered rings such as XXII, including one in which
an alkyl carbon atom has been metallated (XXIII)

ryL\'R
79
o-r"N-O I . . CI
",Au
CI-Au-CI
(47). Although it has not been commented on, the role
of the solvent must be critical here, in allowing the
escape or, more probably, the solvation of the liberated
CI I I HC\'
CI CI CI
A versatile method involving exchange of organic
XVIII XIX groups has been developed. Reaction of [AuC12r with
thallium(I) acetylacetonate produces [Au(acacl-]"

0 (XXIV). This complex reacts with organic molecules

having a moderately acidic hydrogen (HR) to liberate

6- Lc
I
1
CI
acetylacetone and form the corresponding [AuR 2r (48).
For instance, the ethynyl complex [Au(C=CHhr is
readily made this way (49); as the [N(PPh3h]+ salt, this
anion is much more stable than previously reported
(50). Simple gold(I) alkynyls are still made by the
XX XXI traditional method (36) which was effectively the
reaction of [Aubrj]" with HC=CR in the presence of
consistent with the failure of the lithium derivatives of sodium acetate. Similar proton-elimination reactions are
these and similar ligands to react with [AuC14r (43); used to prepare the substituted derivatives LAuC=CR
presumably the organolithium is chelated, again from LAuCl (see, for example, references 51-55);
discouraging the formation of the Au-N bond. alternatively, [AuC=CR)]n is treated with the ligand
Solvent effects are also important in direct auration (56).
reactions of aromatic systems by gold(III) halides. The
first arylgold derivative, [AuPhC1 2b reported in 1931,
was obtained by direct reaction between benzene and
AU2C16 (45). Alkyl benzenes would also react but not
benzenes with potentially coordinating substituents;
for instance, azobenzene gave XIX. More recently it

The unusual compound III is prepared by

bromination of a gold(I) derivative of

~
/, -O sryryldiphenylphosphine (XXV). Oxidation occurs
Me N N rapidly at the gold atom to give XXVI which
Me I
Au-CI
CI
I
CI
(OC)5M[C(NM e2)OEtJ
HAuCI 4 I
CI-Au-C
,NMe2 (5)
XXII (M = Mo, W)
I 'OEt
XXIII CI

.... CI
,Au
",N
OC~ PhNHz
CI-Au-C
,NHPh
(6)
~ C, 'NHPh
"N
'Au
"'CI

8 @ GoldBulletin 1997, 30(1)

 2LiR (Ph 3P)AuCI
[Ph zP(CH 3)zl+ - U[PhzP(CHz)zl - - -

Ph3P
CICHzC(O)NMez [Ph 3PCHC(O)NMe zICI
~NaH
Ph3P = CHC(O)NMez
<, CIAu(CH2PPh~
o
II
(tht)AuCI/
,/ (8) (9)" 0
II
0
II
l+
C-NMez MezN-C C-NMez
"
CI-Au- CH ,HC-Au-CH"
, PPh3 Ph 3P
/ ' PPh3

undergoes slow rearrangement to III (9, 57). as the deprotonating agent (Equations 9-11) (18,48).
Analogous reactions occur with the corresponding A range of methanide complexes can be obtained by
allyl-substituted phosphine (9). making use of the basicity of an ylide carbon atom
Carbene complexes can be obtained by (Equations 12-15) (18,58),
transmetallation, involving metal carbonyl derivatives Finally, many of the hypervalent compounds are
(Equation 5) (14) or by nucleophilic attack on an made by an ingenious reaction in which a
isonitrile (Equation 6) (13). Ylides are usually obtained dimethoxyboryl compound undergoes displacement of
by deproronarion of a methyl phosphonium salt, using the B(OMeh group by an AuU group and
butyl lithium or sodium hydride. They are strong simultaneously becomes transformed into a BF4- anion
ligands and readily replace halides, or other weakly by the addition of CsF (in THF solution) (Equations
bound ligands from gold(l) complexes (Equations 7,8) 16, 17) (25, 26).
(22, 48). In some cases a ligand already bound may act

Phz Ph z
P-Au-P
Ph 2PCH2PPh2 /.' '0\
HC'. ',CH (lO)
\:. ./
P-Au-P
Ph z Ph z

o
II
C-NMez
l+
(II)
Ph3P-Au-CH ,"
PPh3

(l2) (Ph 3P)Au(acac)

Ph 3PAu" "C-NMez
oII l+
C
Ph 3PAu / ' PPh3

@ GoldBulletin 1997, 30(l) 9

 Ph 2 Ph2
P-Au-P
j' .~
He:: .... CH
\. :j
P-Au-P
Ph 2 Ph2
(tht)AuR / ~ [LAu(tht)]CI0 4

Ph Ph / (13)
(14) ~
RAu /:
2
P-Au-P
..~
2

LAu /C.
Ph 2 Ph 2
P-Au-P
..~ H
12+
'c.: ': c:.. . . H 'c:' ··.C.. . . .
w...... \:" :( <, AuR H.. . . . \. :/ <, AuL
P-Au-P P-Au-P
Ph 2 Ph 2 Ph 2 Ph 2

(15) ILA"(~~I
Ph 2 Ph 2
P-Au-P 2+ 1
LAu /.: ".\ .... AuL
'c: . c"
LALf \;. :/ <, AuL
P-Au-P
Ph 2 Ph 2

An increasing number of applications for gold

CONCLUSIONS compounds can be envisaged, and many of these are
based on the organogolds; these will be discussed in a
This survey shows that, despite the enormous variety second article. These applications depend on the ways
of types of organogold compound now known, some in which organogold compounds react, and these
apparently rather exotic, their coordination numbers reactions will also be surveyed.
and stereochemistries obey simple rules: gold(I) is
two-coordinate and linear, and gold (III) is four
coordinate and square planar. While other structures ABOUT THE AUTHOR
are known (a few three- and four- coordinate gold(I)
complexes, a very small number of five coordinate Dick Parish is Reader in Chemistry at UMIST and has
gold(III) complexes) they do not appear in a long-standing interest in the chemistry of gold,
organogold chemistry except perhaps as reaction particularly of compounds with actual or potential
intermediates. medicinal interest, and in the application of Mossbauer
spectroscopy to coordination chemistry, including that
of gold.
LAuCI

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LAuC!
Goldorganische Verbindungen, (ed. H.
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