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Is Gold Chemistry a Topical Field of Study.

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Is Gold Chemistry a Topical Field of Study?
By Hubert Schmidbaur[*]
The question raised in the title of this progress report is answered point for point with
an emphatic “yes”: Ranging from metallic gold, u i m clusters of gold atoms in low valence
states, compounds of Au’, Au”, Au”’, and AuV, organogold derivatives, ylide and carbene
complexes, to the catalytic activity of gold it embraces a long-neglected area of chemistry
holding promise of many a discovery.
1. Introduction
1.1. Historical
Metallic gold has from antiquity been regarded as the very
epitome of material value. The continuing practice of striking
coins in this metal (if not as legal currency, then as an inflation
hedge and a speculative form of investment), the still at least
partly valid relation between actual currencies and national
gold reserves (Fort Knox!), and finally the undisputed preference for gold as the basic material of jewelry are an obvious
reason for and a clear manifestation of this idea. The idea
therefore grew up not only among laymen, but also among
chemists, that gold should be ascribed a special place among
the elements. It is not uncommon to encounter the prejudice
that occupation with gold chemisrry reveals an inability to
grasp reality since the use of gold for purposes other than
those mentioned above is inconceivable. The question of “relevance” is therefore best disregarded in this context.
Continuing in this vein, a general survey of the principal
combinations of the element does indeed show that in most
chemical systems elemental gold is distinctly favored thermodynamically over its compounds‘’]. Nature itself has predestined gold’s role as a noble metal in the truest sense of the
word. Thus apart from its combinations with strongly oxidizing halogens, gold chemistry is a chemistry of metastable
compounds and leads almost invariably-whether desired or
not-to elemental gold as the essentially stable species. With
few exceptions the metal also occurs as elemental gold in
its natural deposits[’].
1.2. The Present Situation
Such a standpoint nevertheless overlooks a number of
aspects which present this neglected area of inorganic and
organometallic chemistry in a much more favorable light.
I t should first be mentioned that the price of gold is currently
much lower than that of many so-called “rare” metals. For
instance, platinum, palladium, iridium, rhodium, osmium, and
ruthenium are traded at a price much higher than that of
gold. Yet these metals and their compounds are frequently
utilized in practice and are still under intensive study. Moreover, gold is on no account one of the rarest elements and
its abundance far exceeds that of most of the above noble
metals. Its scarcity may therefore merely be a result of hoarding
reserves.
In addition the uses of gold are no longer restricted to
coinage and jewelry, but are steadily increasing in number
and scope. An example that has received considerable publicity
through spectacular photographs is the coating of aerospace
equipment with a bright gold plating; and another one is
the gold coating of radiation-inhibiting window panes characterizing the appearance of numerous modern buildings. Gold
is also used in collectors for solar energy and is predicted
to have a great future in that field.
Even more manifold but less evident to the casual observer
is the role of gold in the microcosm of the latest generation
of electronic equipment; many components and circuits would
be unthinkable without gold.
An old rule of ccrtalj2,st research appears to regard gold
as a black sheep among the noble metals, for it has so far
found practically no catalytic application. The activity of the
neighboring elements platinum and palladium underlines this
shortcoming. However, recent findings suggest that these ideas
may soon be due for revision.
Finally, mention should be made of the use of gold in
medicirze and dentistry. Although many attempts have been
made to develop new methods for treating polyarthritis, the
classical field of application of gold therapy, we still cannot
dispense with this “chrysotherapy”. It remains a topic for
research to discover gold compounds in which therapeutic
action and heavy metal toxicity are related as favorably as
possibleL2].
This brief survey should demonstrate that research into
gold chemistry often has a very realistic basis. Most of the
new working forms of gold are obtained ria gold compounds,
and a deepening of our understanding of their chemistry is
therefore highly desirable.
An attempt is made in the following to trace advances
and developmental trends with the aid of important contributions to gold chemistry dating from the past five years, and
to stimulate further study of this most enchanting material.
No claim can be made to completeness, and the choice is
necessarily subjective. Organogold compounds are treated
separately (Section 7), an approach justified by the unparalleled
development of this field of gold chemistry[31.This promotes
clearer understanding by providing an opportunity for a more
detailed examination of various aspects.
2. Elemental Gold and Clusters of Gold Atoms in Low
Valence States
2.1. Gold Vapor and Gold Metal
[*] Prof D r H. Schmidbaur
Aiioreaniscli-chciniachcs Instittit der Technischen Universitiit
Arcisstrasse 21. D-X000 Miinchen IGermany)
728
The three states ofaggregation of elemental gold were studied
in considerable detail at a very early stage“’. A very remarkable
result is that, above the boiling point of the metal, gold vapor
consists primarily of dimers Auz characterized by one of the
largest dissociation energies known for homonuclear diatomic
molecule^^^^. The experimental value ED= 232 kJ/mol exceeds
the dissociation energy of almost all halogens and interhalogen
compounds of type A2 and AB.
There has therefore been no lack of attempts['-'] to trap
the Au2 species by complex formation; simple donors should
give products ( 1 ( I ) isoelectronic with the mercury(\) compounds ( I b ) :
A Au-Au
Au-Metal
Hg-Hg2@
+
2
+
2 :Xo
:L
--
L-Au-Au-L
(la)
X-Hg-Hg-X
lIb)
The ligands L tried were mainly phosphanes R3P or sulfanes
R2S. Astonishingly, not a single complex ( 1 a ) has yet been
isolated, or even detected. The same applies to reduction
experiments on gold compounds in solution, which have long
been known to afford a large variety of gold colloids[']. However, the occurrence of discrete, well-defined polyatomic aggregates, i. e. clusters, has recently been detected. The metallic
nuclei of these clusters which are enclosed by a sheath of
ligands may be regarded as a link between the particles found
in the metal vapor and the practically infinite aggregates
of the molten and the crystalline metal. N o other metal has
yet been found to form as many different homoatomic clusters
as gold. A knowledge of the structure of such species can
provide valuable information pertaining to metal nuclei, their
formation and their growthl5I.
Metallic gold crystallizes in a cubic face-centered lattice,
with each metal atom being surrounded by 12 equidistant
neighbors (Au-Au distance 288.4 pm). The mechanical and
electrical properties of this soft, readily workable metal having
good electrical and thermal conductivity can be attributed
principally to this lattice type (m.p. 1064.43"C, b.p. 2860°C).
The smallest metal aggregate containing two atoms in a
low oxidation state ( < 1 ), the Au2 unit, was first discovered
by Nesmeyanoc et a/. in organogold compounds of type (2)['].
However, this is not the simple unbridged form [cf. ( I a ) ] ,
but the triatomic CAuZstructural unit in which a tetrahedrally
coordinated C atom serves as a bridge between two gold
atoms in direct contact. Such species are formed on reaction
of RAuL complexes with AuLQ ions:
+
A~-L@
Dimroth et a/.[' 'I recently postulated a structure containing
an Au3 unit for a compound formed on reaction of the AuCl
with sodium
complex of 2,4,6-triphenyl-k3-phosphorin['21
methoxide. Determination of the relative molecular mass indicated the trimer, and spectroscopic data accord with structure
(5).
2.2. Gold Clusters
R-AU-L
Compounds have also been found in which two gold atoms
not linked together are bonded to the same C atom. While
a first series of examples[81 closely resemble those of type
(2), a second class can be derived from the carbodiphosphoranes R3P=C=PR3[101. The latter readily form 1 : 2 complexes
with gold(i) reactants, according to
-
L
A;
R:!
o
Au
'L
Ph
The next larger cluster unit, a Au6 octahedron, was first
discovered in the group of gold compounds studied in great
detail by Ma/utesta ef a/. during recent years[l3].They were
prepared by careful reduction of phosphane complexes LAuX
(X =(pseudo)halogen, L = phosphane) and the products isolated by employing special crystallization techniques. Some
of the products have the composition [ A U ~ L ~ ]+
~ '2X0, thus
implying a formal oxidation state of +0.33 for the gold atoms.
f2)
R is initially a triply coordinated C atom of an aromatic
or olefinic group which achieves the coordination number
4 in the course of the reaction: R=C6H5, C6H4CH3,
CHz=CH, ferrocenyl (Fc), etc'. The last-named example [ ( 3 ) ]
has been confirmed by an X-ray study['].
The Au-Au distance is 277 pm and is thus shorter than
in metallic gold. (Compounds containing Au:'
units will be
considered in Section 4.)
729
The structure was determined by X-ray analysis on ( 6 u ) .
The Au-Au distance of ca. 300pm in the cation is longer
than in metallic gold!
The same reduction, usually carried out (like many processes
yielding gold colloids) with alkali tetrahydridoborates, affords
as ' a further type
products of composition [ A U ~ L ~ ] ~ ' . ~ X
of cluster. Once again the gold can be assigned an average
oxidation state (+0.33), but structure ( 6 b ) shows one of
the metal atoms to occupy a distinctive central position. The
metal nucleation is clearly appreciated, even though the coordination is initially only 8. The Au-Au distance (cu. 276pm)
is already approaching that in the metal['"].
demonstrate that up to three gold atoms can be bonded
to a metal center:
3. Compounds of Gold(1)
3.1. Simple Halides and Halo Complexes
Among the gold(])halides, the chloride, bromide, and iodide
have long been known, but only the structure of the last-mentioned halide had been adequately characterized[221.Only
very recently has the crystal structure of AuCI been studied
in two laboratories and fully elucidated. X-Ray diffraction
analysis of single crystals prepared by chemical transport
indicated the angled chain structure, as also occurs in Aul;
however, the bond angle at the chlorine is seen to be considerably greater, and the X-Au-X
unit is expectedly considerably
:
extended[231
/c1\A u
In clusters of formula [Aul 1L7]3'.3X'
a coordination
number of 10 is achievedr15"J,with Au-Au distances of en.
270(central) and 290 pm (peripheral)and an average oxidation
number of only f0.27. The nucleation in ( 6 c ) has therefore
almost reached the arrangement in the metal. Knowledge
of the precise geometry of the atomic arrangement permits
an approximative theoretical treatment of the electronic configuration['5b!
P
The numerous complexes displaying direct contact between
the atoms of gold atid other metals also include clusters, of
which those involving Li, Cu, or Zn warrant particular mention. The structures proposed contain metallic units reminiscent of the structural components of alloys[16a.bl:
Analogous copper and silver compounds are also known" 6 c J .
Discrete gold-transition metal bonds not leading to clusters
occur in many carbonyl complexes. The following examples
730
Au/C1\ A u
A d
'c1/
'c1/
Vibrational spectra in the long wave region were reported
almost simultaneously which provide more detailed information about force constants and bond orders in gold(i) halides.
The hitherto unmeasured bond angle at bromine in AuBr
was also
Earlier indications for the existence of halo complexes AuXF
were confirmed by isolation and vibrational spectra of tetraalkylammonium salts such as [(C2H5)4N]'AuX7, X=C1, Br,
I[261. The same type of compound was studied in dimethyl
sulfoxide solution by electrochemical methods[27J.An example
of the X-ray elucidation of the linear triatomic BrAuBrQ
unit is provided by the structure of bis(di-rz-butyl-dithiocarbamato)gold(rir) dibromoaurate(i)[281.In contrast, it proved
impossible to detect AuXY in rnolrrri gold(i) and alkali halides.
Pertinent melt studies of importance for electrochemical gold
coating of surfaces resulted in d i ~ p r o p o r t i o n a t i o n ~ ~ ~ l .
Gold(])halides are good complexing agents. In recent years
attention has been focused mainly on complexes with sulfur
and phosphorus donor ligands. However, a facile new synthesis
has also been found for the carbonyl complex first prepared
over 50 years ago[301:
H,O@AUC~+
,~ 2 CO
sD('1z
3 HC1
+
SOz
+
COCl2
+
Au(C0)Cl
Although thermolabile, this carbonyl derivative, which readily dissolves in organic solvents, is a versatile starting material
for the synthesis of other Au' complexes since the C O ligand
can be replaced with great ease[311.The exceptionally shortwave v(C0) absorption of the compound (2158 cm- ') likewise
indicates weak interaction between ligand and metal
atom130.311
Gold-halogenvibrations were also closely examined specifically on pyridine complexes[321and constitute an important
part of most publications about sulfide and phosphane complexes.
The complex chemistry of gold with pseudohalogens has
been surveyed only recently[33.341.
3.2. Sulfur Compounds
Early interest was shown in compounds of sulfur and gold
because they were employed for thermal production of gold
coatings on ceramics, porcelain, glass, and metal (and later
also plastics). This concerns less the pure sulfides than organosulfur derivatives. Incidentally, gold is the only metal not
to react directly with sulfur!
Apart from Au2S, the nature of gold(]) sulfides and thiolates
having the formula Au2Sn and AuSR, respectively, remains
largely u n e l ~ c i d a t e d [ ~ ~Valuable
. ~ ~ ] . information has been
obtained, though, from some phosphane complexes of these
compounds. For instance, a well-defined bis(phosphane)
complex of AuzS ( 7 a ) is formed from trimethylphosphanegold chloride and H2S[371.Closely related are the complex
thiolates ( 7b)-(7e)[37-391.
S
A d A
' ",
(CH3)3P/
P(CW3 (7a)
Such gold complexes are of importance in the extraction
of the noble
Another series of compounds is derived from phosphane
su/fides and selmides: typical examples are[38,49. 501:
In the yold/se/enium/tel/irr.ium system the new phases AuSe
and Au2SeTe were d i s ~ o v e r e d ' ~ ~ ] .
Ferrocene thiolate occurs as a bridging ligand in the gold
complex (/0)15'I.
C S H , - S { A ~ P ( C ~ %})z~
Gold atoms are also found as "ligands" of chalcogerioniurn
centers in the complexes [(LAu)~S]'X~,which are accessible
with surprising ease riia silyl sulfide precursors[521.Triaurioselenonium salts were obtained in similar manner[371:
( C H3)3P-A U-SC 2H5 I 7 b )
( C H ~ ) ~ P - A u - S CC( H3)3 / 7 C j
( C sH5)3P-A U-SC H2C gH5 I 7 d )
( C H3)3P-Au-SC H2CH2S-Au-P( C H3l 3
3 R3PAuC1
(7 e )
+
-
(CH3)3SiSeSi(CH3)3
2 (CH3)3SiC1 +
[ ( R3PAu)3Selo C1'
Compounds having the composition and presumed structure (8) have been prepared for therapeutic purposes[401;
( 8 a ) has antiarthritic properties.
( C zH5) 27-C H2-C H 2-S
Au
I
S-CHz-CH2-b(
(80)
I
Au
C2H5)~
[
(c6 % )
ztic
H2-C H 2 - 7 ( C d 5) 2
Au
I
S-CH2-CH2-S
(8b)
I
I
Gold(1) salts also form stable complexes with thioureas,
which, having a ligand ratio of 1 :2, are formulated as ionic
compound^[^'^ :
Unlike the silylthio derivatives, siloxy derivatives of Au' do
not suffer heterolysis to give oxonium
compounds
C6H5,etc. are stable.
such as R ~ P - A u - - O S ~ ( C H ~R) ~=CH3,
,
However, Nesniejanor et a/. have described examples of triauriooxonium salts [ ( R , P A U ) , O ] @ X ~ [ ~ ~ I .
Bridged conip/eses having bidenlate suyur or se/eniuni /igtrnt/s
Monovalent gold has a pronounced tendency to form sulfur
complexes, in which two metal atoms of coordination number
2 (and with linear configuration of their ligands) are components ofan eight-membered ring. The oldest example, whose
structure originally defied explanation[551,is probably the
gold([) trisulfide anion AuSY shown by recent findings to
require formulation as AU~S;':
2 0
S-Au-S
They are of interest for analytical purposes. Analogous bonding has meanwhile been established for the classical thiosulfate
complex (9) by X-ray analysis[421:
Na3[03SS-Au-SS03] ' 2 H 2 0
(9)
Like the corresponding silver complex, this coordination compound played an important role in the infancy of photography,
for which products with gold toning were character is ti^'^^^.
It was also used for treatment of arthritis, tuberculosis, and
leprosy[44'.
The complex chemistry of the Au' ion with thioethers is
Extensive, but has so far provided few surprises. Numerous
compounds have been characterized by spectroscopy, e. g.
refs.[45 - 4 7 1 .
This compound was soon joined by Au' dithio-phosphates
and -phosphinntes whose dimeric nature has been confirmed ;
X-ray data are also available[561.
The dithiophosphates are suitable as additives to lubricants,
being soluble in mineral oils and displaying novel lubricating
phenomena by deposition of very fine noble metal coatings
on mechanical and thermal stress. Crystal structure determination shows the diisopropyldithiophosphate ( I 1 ) to be a
731
polymer containing a chain ofgold atoms; like the dithiophosphinates ( 1 2 ) it exists as the dimer in solution[571.
r
-Au
1
&Au
-Au
-A-u
L
&AU
-AU -
-In
Owing to their ready solubility and volatility, the dithiophosphinates ( 1 2 ) have been proposed for gas chromatographic isolation and detection of gold[581.
A second class of such sulfur complexes is found in the
Au' dithio(or dise/eno)-carbamates. An example has also been
subjected to X-ray
and others to detailed analytical
and spectroscopic studiesf6'- 621.
,
R\
In compounds having two phosphane ligands, (R3P)2AuX,
the structure is frequently dependent upon the environment.
If X is a good leaving group then an ionic structure [R3PAu-PR3]X will be observed in the crystal, and certainly
in solvating solvents[31.751. In contrast, bis(tripheny1phosphane)gold chloride ( I 3) is not ionic in the crystal and contains
Au' having a coordination number of 3[761.
/s.-A"-s.\
R
N-C<.,>C-N,
R'
S-Au-S
R
The therapeutic potential of the thiophosphate and carbamate complexes has also been proposed for examination, but
no final results have yet been publishedl2].
Trigonal-planar Au' is also found in tris(tripheny1phosphane)gold thiadecaborate ( 14)[771and in the hexacarbonyltantalate ( 1 5)1781whose structure has been confirmed by X-ray
analysis. With less bulky phosphanes and large poorly coordinating ligands X even the AuPT configuration may be
achieved[31 . 7 8 - 8 01
The 1 : 1 complex of AuCl and methylenebis(dipheny1phosphane) has the structure of an eight-membered ring with weak
transannular Au-Au interactions between trigonal planar
metal
3.3. Phosphorus Compounds
In accord with present-day ideas of bonding in metal complexes, Au' as a slightly charged, large, and easily polarizable
metal ion forms particularly stable coordination compounds
with phosphorus (and with sulfur). Very many complexes
of this type are known, mainly with triorganophosphane
ligands. Apart from the commonest types of compound
R3P-Au-X
[ R3P-Au-PR3
1'
XQ
representatives having higher coordination numbers also
existl3' I :
Triethylphosphanegold(i) chloride has recently been proposed for a hitherto unknown variant of gold
It appears to display a number of important advantages over
the sulfur compounds (thiomalate,thiogluconate, etc.)formerly
used almost exclusively[8lbl. The substance has a strong inhibitory action on mycoplasmic infections in uitro[821.
4. Gold(rr) Compounds
4.1. Au'jAu"' Compounds
In the case of the simplest type R,PAuX numerous new
examples have been discovered in recent yearsf3'.63-.691. The
range of compounds extends from the complexes of phosphane
itself (R = H)[701via those of trialkyl-, triaryl-, and alkylarylphosphanes, to those of phosphites (R= OR') or aminophosphanes (R = NR;). These are supplemented by analogous
arsane and stibane compounds. Halide, pseudohalide, carboxylatel7'. 721, and also carbaborane anions ( e .y. 2,3-B4C6H7
and BIOC2HIORB,
R = H , CH3, C6H5)[731
may serve as ligand
The crystal structure of the 2 : 1 complex of AuCl with
methylenebis(dipheny1phosphane) has been elucidated[74a1.
It shows a remarkably short Au-Au distance.
132
Compounds have long appeared in the literature in which
gold formally has the oxidation number +21831.Meanwhile,
it has been found that most of them are actually Au'/Ad''
combinations. Some representatives have been characterized
by X-ray methods, and others by magnetochemistry or spectroscopy. In some cases simple analogies were sufficient:
-
~
Empirical formula
~-~~
Structure
AuSO,
AU~AU~~'(SO~)~
A u O , AuS
A U ~ A I J ~ ~A~UO ~~ A
. U ~ ~ ~ S ~
Cs[AuX3]
C S Z [ A U X ~ ] [ A U X ~X
] .= C I , Br, I
(CbH5CHz)zS AUXZ
(ChHsCHz)zSAuX, ( C ~ H ~ C H Z ) ~ S A U X ~
Au(Hdmg)CI
AuiAu"1(Hdmg)zC12
O I - C ~ H ~ ) Z N C S Z A U C I[ [ ( I I - C ~ H ~ ) Z N C S Z ~ ~ A U ] ~ A U C I ~
-
~
~~
-~
~~
Aiiym.. Chrm. 111i. €11. Engl.
__._
Vol. 15 ( 1 9 7 6 ) No. I2
The presence of Au:'
in place of Au'/Au"' has not been
ruled out in the first two examples.
type of Au:'
compound is described in connection with
organogold compounds (Section 7.5).
4.2. True Au" Compounds
5. Gold(rr1)Compounds
Recent studies have shown there to be four types of compounds qualifying as true gold(i1) derivatives in which all
the metal atoms have the same chemical environment. In
addition to p h t h a l o ~ y a n i n e - A u " [("AuPc")
~~~
and an unusual
carbaborane complex ("Au" c a r b ~ l I i d e " ) [ ~this
~ ] ,class includes
the dithiocarhamates of composition A U ( S ~ C N R ~ first
)~[~~]
described in 1959. The uneven number of electrons (d' configuration of metal!) in these compounds, which are obtained
by conproportionation of Au'JAu"' or by reduction and oxidation, respectively, of Au"' and Au', has been detected primarily
by ESR measurements. A bischelate structure is assumed,
which probably also applies to the selenium analog1871.
5.1. Gold Trihalides and Their Halo Complexes
Gold forms trihalides only with fluorine, chlorine, and bromine. The structure of the trifluoride was long unknown.
It was only the advent of modern improved methods of synthesis and single crystal growth, for which it is no longer
a problem even with such a hard to handle substance as
AuF3, which permitted complete elucidation of its struct ~ r e [ ~In~ contrast
].
to the structure of the dimers of AuCI3
and AuBr3, this compound exists as helical polymers whose
AuF3 units are linked together via fluorine bridges:
It should be pointed out that halodithiocarbamates such as
(16) possess an Au'/Au"' structure (cf. Section 4.1). The dihalodithiocarbamates have analogous configurations, e.g.
( 1 7)[28.88,891
r
m
,
a
116)
117)
The fourth type of Au" compound was discovered in the
cis- 1,2-dicyanoet hylenedithiolates ("muleonitriledithiolutes"),
and is likewise accessible by a variety of synthetic
approacheslgo1.
Gold trichloride, on the other hand, is dimeric in the solid
state, in many solvents, and in the gaseous phase; it numbers
among the most thoroughly studied compounds of gold"'.
A particularly convenient preparation was recently discover,d[301:
2 H,O@AuCl,@
Identification was again accomplished by magnetochemistry
and ESR spectroscopy [ p e r f = 1.85 p~;g=2.009,hyperfine splitting A=41.7G (197Au:
Any remaining doubts as
to the existence of true Au" complexes were finally dispelled
once the nature of these compounds had been established.
4.3. Au:O Compounds
The AuCl complexes of methylenebis(ph0sphanes) undergo
oxidative addition of one mole of halogen to yield formally
a gold complex of oxidation state 11. Mossbauer and ESCA
investigations have confirmed this proposal and the following
formula is therefore assigned[911:
+
+
2 SOClz
+ 2
SO2
+
6 HC1
+
AuzCl6
Furthermore, the first synthesis of a well-defined oxide halide
A u O C I [ ~has
~ ] also been accomplished, and the enthalpy of
formation of the oxide A11203 could be accurately determined'941. Both compounds are hydrolysis products of the
trihalides.
Gold(1rr) sulfide, selenide, and telluride halides are discrete
phases in the gold/chalcogen/halogen system. Typical
examples are AuSeCI, A u S ~ B ~ ' [I , ~ ~AuTe2C1,
",
and
A u T ~ ~ IIn[ the
~ ~gaseous
~ ~ . phase, AuC13 and FeCI, form
a complex A U F ~ C I ~ [ ~ ~ ] .
The structure of gold tribromide, likewise a well-known
compound, was determined only recently[971; it closely resembles that of the trichloride.
C1\
/C1,
/C1
Au
\c1
These products are diamagnetic, as expected, but a crystal
structure determination has not yet been carried out. A new
l
Br,
/Br\
/Br
Au
Au
Br' \ B r / \ B r
Crystallographic data were also reported for Rb[AuBr4] and
Rb2[A~2Br6][981.
Such halonurate coniplexes, and especially the tetrachloroaurate unit, are components of numerous salt-like compounds.
Their structure and bonding are k n o ~ n [ ~ ~ .-A"UCI?
~ ] will
occur not only in crystalline compounds but also in molten
saIt~f~~1.
133
Syntheses and structural elucidations of tetrafluoroaurates
are almost all comparatively recent. The square-planar anion
structure was confirmed for a series of alkali and alkaline
earth salts. The potassium compound crystallizes in the KBrF4
type" '3.
M'[AUF,]
M I' [ ALIF 4 12
M ' = L i , N a , K , Rb
M " = M g , Ba
Among the mixed noble metal haloaurates, the particularly
attractive structures of the complexes Cs2AuAgC16 and
(NH4)6A~3Ag2Clldeserve special
x... &
...,
.
...+
..._
%%
..
As expected, gold trihalides from stable complexes with
nitriles" 221, amines" 231, phosphane oxides and sulfides[38.1241,
and with triorganophosphanes. Trichloro(tripheny1phosphane)gold has been studied by X-rays and shows the expected
square-planar ligand arrangement" 251. In contrast to Au'
halides, those of Au"' also form complexes with azo compounds, which have an asymmetric structure" 261:
Older literature records the formation of "fulminating gold" on
ammonolysis of tetrachloroauric acid. This complex reaction
is currently being reinvestigated, and the stability constants
of the Au"'-ammine complexes have been determined['27a1
and the crystal structure of [ A U ( N H ~ ) ~ ] ( N O
solved['27b1.
~)~
The Au"' complexes of amino acids[128a,'I, aldimines['28c1,
and tetracyclines[' 28d1 cannot be discussed in the present
report.
6. Gold@')Compounds
They are characterized by alternation of AuCI? with AgCl?
and Ag2CI$e groups [cf. also Cs2(AuC12)(AuC14)in Section
4.11.
The mechanisms of reactions of the square-planar AuCI?
ion with various substrates have seen several attempts at
elucidation; however, the individual reaction sequences often
differ considerably[''' ' 'I and thus defy generalization.
Gold(n1)pseudohalides have already been surveyed[33.' I 2 . 13!
Until a few years ago gold in the oxidation state $ 5 was
unknown. Only in connection with the chemistry of noble
gas halides did it become possible to accomplish the surprising
synthesis of hexafluoroaurates(v); careful study left no doubt
as to this new d6 valence state of gold. Meanwhile, their
synthesis is possible without the noble gas fluorides since
other fluorination methods also lead to the desired result['291:
~
'
5.2. Compounds of Au"' with Sulfur, Phosphorus, and Other
Elements
Gold(ll~)halides also form complexes with thioethers, but
they are less stable than the gold([) compounds. Fitting
examples are[46*47,
' 141:
The AuFF ion is octahedral and corresponds to PtFie and
other long-known analogous anions. Very recent work has
extended the series of its salts to include K~F[AuF~]['~'].
Uncomplexed gold pentafluoride AuF5 is formed as an orange
powder on vacuum pyrolysis of the KrF@-' or 0:-hexafluoroaurates" 301.
7. Organogold Compounds
7.1. Alkylgold(i) Complexes and Dialkylaurates(1)
Corresponding coordination compounds exist with diphenylthiourea[' 151 and dimethyl sulfoxide[' 16], which is presumably
coordinated via the S atom. The thiocarbamates[' ' 'I, dithiomalonamides" ' I, and dithiooxamides" ' 91 have already been
mentioned in part[*'l.
Gold(l1i) fluorosulfare A u ( S O ~ F ) which
~,
does not strictly
number among the gold-sulfur compounds, was synthesized
just a few years ago; its structure has not yet been completely
established" 201.
As for other noble metals, an anhydrous nitrato complex
of composition [ A u ( N O ~ ) ~has
] ~ also been obtained for
The analytical data indicate the nitrato group to
act as a unidentate ligand.
734
Pure, not complex-stabilized alkylgold compounds RAu
have not yet been isolated. However, the number of complexes
derived therefrom is steadily increasing. A tabular summary
of such triphenylphosphane complexes should underline the
broad scope of the investigations performed so far[3'*131-1361.
Atigew. Chriii. I i i f .
Ed. .Gig/. J V d . I5 ( 1 9 7 6 ) N o . 12
In addition to these examples the cyclopentadienyl compounds, which have been shown to possess a fluxional structure
also warrant mention. The ferrowith an A u - C 5
cene derivatives, in which the cyclopentadienyl group is also
aconstituent of the x-complex, represent an interesting variant
of this compound
Nearly all the publications cited contain detailed information about the spectroscopic properties of the RAuL complexes''391. The simplicity of their NMR spectra proved to
be particularly useful in the study of their reactions[131.132.1 3 4 , 1 3 5 1
It was already known that R-Au-L
complexes react with
alkylmetal compounds presumably forming R-Au-R'
a n i ~ n d ' ~ ' ] ;however, these species could not be directly
detected. Recent studies have now demonstrated that such
products are stable both in the presence of stabilizing phosphane
and in solvate-free
up to
room temperature and even beyond. An example of the firstnamed case is:
CH3AuP(C6HJ3
+
CH3Li
-
(CH3)&uP(C6H5),Li
The structure of the product is not accurately known114'].
If effectivecoordinative saturation of the lithium ion is ensured
then the thermal stability increases sharply and salts are formed
which are made up of linear dialkylgold anions and chelate
cations, e.g.['421:
[ { ( CH3)2NCH2CH2N( CH3)2}Lil@ [CH3-Au-CH3Ja
The compounds obtained in this way react with alkyl halides
to form trialkylgold(iii) complexes which decompose with
reductive elimination of alkane under suitable condit i o n ~ ~ 1' 4~3 1' . ~They
,
are therefore suspected to play a role
in the formation of C L C linkages catalyzed by gold(i) salts,
which start from alkylmetal compounds and alkyl
Copper(i) salts are used more frequently for this reaction.
The R-Au-R~ ions correspond to the neutral mercury compounds R-Hg-R.
Analogous reactions involving more complex alkyl groups
attached to the gold atom can also lead to isomerization,
one such process is the rearrangemainly in the Au"'
ment of a tert-butyl group into an isobutyl group according
to 11431.
7
H3
( CH3)3C-Au-L
---+
f: H3
(CH3)zC HC H2-Au-L
I
CH3
I
c H3
The rate of this rearrangement corresponds to a first-order
reaction with respect to the concentration of complex, but
is independent of the phosphane concentration [L]. Hence
a predissociation to free L and trialkylgold is deduced. NMR
measurements also suggested an associative mechanism to
be unlikely for ligand substitution of R3AuL complexes['31';
preparative experiments nevertheless demonstrated the ready
substitution of L in the presence of an excess of competing
ligand~~'~~~.
Alkylgold(i) complexes, but not alkylgold(iir) complexes,
surprisingly react with thiophenol by a radical
mechanism139.1461.
7.3. Alkylgold(lrl) Complexes and Tetraalkylaurates(ii1)
Like free alkylgold(1) molecules, those of trialkylgold(1ii)
are unknown. The number of complexes has rapidly increased,
however, and many examples have been examined in detail.
In addition to the R3Au.L type i t ~ e l v ' ~1 3' .4 , 1 3 5 1 , the monofunctional derivatives R2XAu.L are particularly interesting;
they generally exist as the cis
Most of these
new compounds were obtained by conventional synthetic
methods or as products of oxidative addition to alkylgold(1)
complexes (cf. Section 7.2)[14'- '451.
A special case is seen in the formation of heterocycles by
halogenation of an olefinic precursor and alcoholysis of the
intermediate with ring expansion; this reaction is almost without precedent. The structure of these compounds has been
established by X-ray
7.2. Oxidative Addition of Alkylgold(1) Complexes and
Mechanistic Aspects
Methyl iodide reacts with methyl(trimethy1phosphane)gold(i), giving ethane and iodo(trimethylphosphane)gold(i) rin
unknown intermediate^"^^^. The initial step was interpreted
as an oxidative addition to give an unisolable product. Subsequent investigations with other ligands then showed the reaction to take the following
CH3Au. L
+
(CH3)zAuI. L + C H ~ A U
' L
(CH~)~A
U --+ C2H6
' L
C H ~ A UL
.
+
-
CH31 -+ (CH3),AuI. L
CH3I
+
(CH3)sAu ' L
+
L 'AuI
CH~AU
' L
CzH6
+
Tetraalkylaurates(1rr) have been synthesized in similar manner
to the defined dialkylaurates(1). Coordinative saturation of
the cation (Li+)by polydentate ligands enhances the stability
of the salts to.such an extent that they can be isolated in
pure form and can also be stored above room temperature11421.
The following formulas give some indication of typical alkylgold(iii) compounds1'3 2 . 1 4 9 - ' "I:
L .AuI
Thus CH3AuL unexpectedly has a methylaring action on the
dimethylgold(iii) iodide complex, giving the ( C H 3 ) 3 A ~
complex which then decomposes with elimination of ethane.
This final step is still unexplained, since pure (CH3)3AuL
is stable under the reaction conditions, and the by-products
apparently catalyze its reductive
735
7.4. Arylgold(i) and -gold(iii) Compounds
Arylgold compounds were practically unknown until very
recently[31;the first well-characterized examples date from
1972" 'I. Meanwhile, considerable advances have been made
in their preparation by improvement of the phenylation process[153-15s1,
in particular by the use of phenylthallium reagents" 5 6 . l 571.This applies above all to perhaloaryl derivatives.
A selection of equations shows the synthetic methods used
and the structures of the products, which have been confirmed
in part by X-ray methods" 58. I 591.
C6H6
+
AuC13
+
- HCI
The prototype of this class is methyl(trimethy1phosphoniomethylide)gold(l) and its homologs and the corresponding
phosphane compounds and bis(y1ide)gold salts['66a1.
These substances arise from suitable gold(i) precursors by
substitution of phosphane or halogen. Gold(l1r) ylide complexes are obtained analogously from trialkylgold components[166bl:
Y1
(it-C~H7)pS+( / ~ - C ~ H ~ ) ~ S - A U - C I
I
C6H5
The first case is an example of the classical "auration"
of aromatic compounds according to Khurusch and Isbe/l[1601,
which frequently gives poor results in other cases. Phenylgold(1)
complexes such as C6H5A~P(C6H5)3['551
were described by
Pereuulooa et
Their orrho/purci substituted homologs
display a pronounced thermal stability[I6'. 1621, e.g.
The structure of aurated pyridine[163],like that of 1-pyrazolylgold(^)['^^^ which is also trimeric, is a particularly attractive
example of the wide range of structural variation.
The bis(ylide)gold(iir) salt (18) can be transformed into
the bis(ylide)gold(I) salt ( 1 9 ) by thermally induced reductive
elimination of ethane[166b1.A further type of gold-ylide
complex is accessible by transylidation in the presence of
an excess of ylide base. There result cyclic compounds in
which two gold atoms have a linear arrangement of
ligands['66'1:
LAuX
+
2 (CH3)3P=CHz
-L
- [(CHhP]X
Such heterocycles have been prepared with various substituents on the phosphorus atom, and an arsenic analog has
also been synthesized with (CH,),AS=CH,['~~~.The crystal
structure of the corresponding copper compound is already
known[l6*].Recently, the structure of the ethyl-substituted
gold analog was also determined" 671.
7.5. Gold(i,ii,iii) Ylide Complexes
The considerable number of compound types and their
manifold structural phenomena justify devotion of a separate
section to the gold derivatives of phosphorus, arsenic, and
sulfur y l i d e ~ [ l ~The
~ ] .compounds are distinguished by exceptional thermal stability and strongly modified chemical reactivity.
CH3-Au-CHz-P( C H3)3
( C H3)3Si-C Hz-Au-CHz-P( C H3)3
[ ( C H3)3P-Au-C H2-P( C H3)3IC1
[ ( C H ~ ) ~ P - C H ~ - A U - C H ~CH3)3IC1
-P(
736
H
H2
H3C,,,
Cku-C
CH3
*AS{
\AS'"'
H3C'
C-Cu-C'
'CH3
Hz
HZ
H3C.,%
As\
H3C'
H
Hz
,C?Au-C
CH3
'AS8
C-Au-C'
'CH3
HZ
H2
On reaction with halogens, the above heterocycles initially
afford bicyclic derivatives (20) having a transannular Au-Au
bond" 66c1. A crystal structure analysis is available for the
ethyl compound['691.Once again AuiO units, and thus gold
atoms in the formal oxidation state + 2 (cf. Section 4.3), are
encountered. On treatment with methyl iodide, oxidative addition proceeds as with halogen to give a product (22) which
yields (23) on methylation"66'1.
Further halogenation of the dihalides (20) finally results in
rupture of the Au-Au bond to give the Au"' heterocycle
A i y n r . Cliriii. I r i r .
Ed.
EiiyI.
J Vol. I5 ( I Y 7 6 ) No.
I
7.7. Reactions of Alkenes and Alkynes with Gold Compounds
Studies by Huttel er u / . [ ' ~ ~ have
I
shown that above all
gold(1) salts can form x-complexes with a whole series of
olefins, some of which display pronounced stability. These
findings have mainly been surveyed on an earlier occasion[31.
In more recent studies, interest has been focused on more
specific problems, e. g. on the reaction between hexamethylDewar benzene and gold trichloride, which leads to an AuCl
complex (24) of the hydrocarbon and to the tetrachloroaurate of its monochlorination product (25)" 79b1.
(21). Mossbauer and ESCA spectra confirm the different
valence states of the metal atoms in the products (20) and
(23)"701.
7.6. Carbene Complexes of Gold
In the course of the rapidly developing chemistry of metalcarbene complexes, Au' and Au"' have been examined to
establish their suitability as coordination centers for carbenoid
ligands. Thus was born a new subdiscipline of organogold
chemistry. The first examples of such compounds were obtained
by addition reactions with isocyanides" 71. l 7 * l or their com-
The interaction of acetylenes with gold halides leads in the
case of dimethylacetylene" *01to x-complexes, e. g . (261, which,
however, rearrange into o-compounds such as (27) under
mild reaction conditions.
I 7 3 - 1 751.
Cyclooctyne reacts with AuBr to give a 2 : 1 complex of
unknown structure which possesses a remarkably high stability" * '1.
X-Ray structural data are available for all types["'b. 1 7 6 1 .
Monoisocyanide complexes form cyclic products with alco-
3 R-NxC-Au-X
+
3 R'OH
-3HX
R'O\
Au@
R
C =N/
Au
R-N'
\\
/C-Au-N\
R = R' = CH3
Cyclooctatetraene forms only a very weak complex (28) with
AuCl; its formation constant was determined as
K =9.1 I/mol['821. Its reaction with fluorosulfuric acid gives
a presumably ionic product:
R'O
A
' u
\C4R'
//
R
A new synthetic procedure for carbene complexes, as shown
in the following equation, is applicable to many metals and
gives very good yields in the case of A U " " ~ ~ :
(28) and AuCI3, as well as COT and AuCI3 (with partial
reduction to AuCI), give an unstable complex of composition
COT.Au2CI4,whose Mossbauer spectrum clearly reveals the
Au'/Au''' combination; an unequivocal structure could not
yet be assigned[1821.
137
In the case of fluoroolefins practically no z-coordination
occurs, either with Au' or with Au"'-instead
insertion or
elimination is observed in all cases reported so far['831:
ZzF,
f
-
CH~ALIL
CH~CF~CF~AUL
F3C\
- " H +
ZFs-CX-CF,
+
/CF3
C=C\
;L
A ~ L
LA^'
=
P(CcH5)s
2 CH~AUL
\iF3C\
/CF3
/C=C,
/CH3
LAu
AU
; L = P(CH3)3
H3C'
\L
In the last example, the structure of the reaction product
was proved by X-ray analysis and by Mossbauer spectroscopy"s4a1 after other proposals had originally been put forward['84bl
With CF,C-CH, CH,AuL and (CH,),AuL give the products LAu-Cx-CF,
and cis-(CH,),AuL-Cx-CF,,
respectively[ 184b1.
The examples of olefin/gold interaction listed above suggest
that this metal could also assume a role as a catalyst in
olefin reactions. Indeed, strong supporting evidence is already
available, for example in the electrooxidation of ethylene at
gold electrodes['851.Current-carrying gold surfaces also catalyze the air-oxidation of propene, the reaction displaying considerable selectivity"861. Tetrachloroauric acid on a silica support catalyzes the hydrogenation of ole fin^['^'^. Hydrogenation of ethylene is catalyzed by HAuC14 in the presence of
SbX5['881.
The recently synthesized gold(1) ketenide A u ~ C ~ O [also
'~~]
appears to show a catalytic activity['901resembling that of
gold([) acetylide""!
I
A final example of a pronounced catalytic activity of gold
has been obtained very recently. A gold film condensed onto
a support material catalyzes hydrogen/deuterium exchange of
alkylsilanes at as low a temperature as 195 K"921.Surprisingly,
however, this effect disappears at room temperature!
In conclusion, reports should also be mentioned according
to which microorganisms are capable of enzymatic dissolution
of elemental gold, and could therefore be made responsible
for leaching out gold-bearing rock and enriching the metal
in concentrated deposits. This "bioorganic aspect" again shows
the kind of surprises to be expected in gold chemistry.
Received: February 5, 1975 [A 119 IE]
German version: Angew. Chem. 88,830 (1976)
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