Polyhedron Vol. 16, No. 1, pp.

1 17, 1997
Copyright © 1996 Elsevier Science Ltd
~) Pergamon Printed in Great Britain. All rights reserved
S0277-5387(96)00190-8 0277-5387/97 $15.00+0.00

P O L Y H E D R O N R E P O R T N O . 63

Metal-metal bond formation in the oxidative addition to dinuclear

gold(I) species. Implications from dinuclear and trinuclear gold chemistry
for the oxidative addition process generally

John P. Fackler, Jr
L a b o r a t o r y for M o l e c u l a r S t r u c t u r e a n d Bonding, D e p a r t m e n t o f C h e m i s t r y ,
T e x a s A & M University, College Station, T X 77843-3255, U . S . A .

CONTENTS
1. I N T R O D U C T I O N TO THE G E N E R A L CONCEPTS O F D I N U C L E A R OXIDATIVE
ADDITION . . . . . . . . . . . . . . . . . . . . . 1

2. G E N E R A L F E A T U R E S OF THE OXIDATIVE A D D I T I O N PROCESS 2

3. OXIDATIVE A D D I T I O N IN D I N U C L E A R A N D POLYMETALLIC SYSTEMS. 4

4. OXIDATIVE A D D I T I O N TO D I N U C L E A R GOLD(I) C O M P L E X E S . 4

5. DOES THE I N I T I A L OXIDATIVE A D D I T I O N INVOLVE BOTH METAL

CENTRES? . . . . . . . . . . . . . . . . . . . . . 6

6. EVIDENCE THAT OXIDATIVE A D D I T I O N DOES NOT FIRST F O R M A MIXED-

VALENCE Aum/Au I SPECIES . . . . . . . . . . . . . . . . 7

7. R A D I C A L I N T E R M E D I A T E S . . . . . . . . . . . . . . . 9

8. OXIDATIVE A D D I T I O N OBSERVATIONS WITH OTHER D I N U C L E A R GOLD(I)

COMPLEXES . . . . . . . . . . . . . . . . . . . . 10

9. IMPLICATIONS O F THE G O D D A R D - L O W OXIDATIVE A D D I T I O N CONCEPT

TO THE D I N U C L E A R GOLD(I) CHEMISTRY . . . . . . . . . . . 10

10. OXIDATIVE A D D I T I O N TO L I N E A R T R I N U C L E A R SPECIES . . . . . . 12

11. S U M M A R Y . . . . . . . . . . . . . . . . . . . . . 14

1. I N T R O D U C T I O N TO THE GENERAL CONCEPTS OF DINUCLEAR OXIDATIVE

ADDITION
M a l c o l m C h i s h o l m stated some years ago, ~ " W h a t one m e t a l can do, two m e t a l s c a n d o b e t t e r " .
T h e r e is c o n s i d e r a b l e evidence t h a t c h e m i s t r y a s s o c i a t e d with m u l t i n u c l e a r m e t a l species 2 can be
significantly different f r o m the c h e m i s t r y t h a t occurs with molecules c o n t a i n i n g only a single m e t a l
a t o m . In their b o o k , C o l l m a n , H e g e d u s , N o r t o n a n d F i n k e have d e s c r i b e d 3 s o m e very interesting
e x a m p l e s involving two m e t a l a t o m s . C h i s h o l m , 4a Balch, 4b'4¢ C o w i e 40 a n d o u r g r o u p 4i'5d have dis-
cussed results involving m e t a l - m e t a l b o n d f o r m a t i o n a n d r u p t u r e with di- a n d t r i n u c l e a r species.
Bosnich ~ d e m o n s t r a t e d with d i n u c l e a r Pd, R h a n d Ir c o m p l e x e s t h a t p r o x i m i t y factors c a n nega-
 J. P. Fackler Jr

19b
CD3 CH3, CD 3 exchange
',.. / ' - - A u - - ~ ....,, 33
"o.. p/"" Au"~p ..o
o .,=Pk__lu_jm-~ 22~

"~" k---Au--/ " ~ x o~o

CH 3 S r ~/ ,,,,~ Au"~ ,,,.
J'P l P~
CD3I /¢X - Br, I ~" ~---Au--J ~ "
o'N~)
5i
/ - - An--%
e,.... "_..,o~
Gold(II) _ $8
#~"P~=. AuJ "~
Sulfur
Rings CF3CH21 ~ (C6Fs) 3

C2H5I~
X Cl,Br, I ~'~ CI6F5
R! ~/ CH3X
X = Br
,Jwo / ' A u " ~ *~ o
**"F Au--~
~ Au-.J
!
" .. x__lA u-/ - x.- t uJ
X 22b C6F 5
X sj
Fig. 1. Reactions of dinuclear gold(I) ylides with various small molecules. A lead paper
describing the chemistry is listed in italics.

tively influence oxidative addition in dinuclear systems in which the metal atoms "were within a
cooperative distance", but not capable of metal-metal bond formation. Stobart 4f examined the
oxidative addition of alkyl halides and halogens to [Ir(/~-pz)L2]2, pz = pyrazoyl and L = CO,
cyclooctadiene or PPh3, CO mixtures. These reactions produce a two-centre two-electron addition
with the formation of a metal metal bond. However, with alkyl- and arylamido ligands, Ahmed 4h
showed that CH3I addition to [IrB(CO)2]2 (B = N H R - or N H £ ) produces a IrIH-Ir~complex, while
I2 gives the metal-metal bonded Ir n Ir" species. Also the oxidative addition chemistry at dinuclear
Pt centres has been described recently in a review by Anderson. 4g
One of the important aspects of dinuclear systems is the ability of the two metal atoms to form a
metal-metal bond, thereby stabilizing a reactant, a product or an intermediate. Alternatively, the
second metal atom may inhibit ~ the reaction of a normally reactive centre, either through steric or
electronic properties or both. Studies in this area with dinuclear gold(I) complexes were pioneered
by Schmidbaur and expanded by ourselves and others, s They have demonstrated a rich reaction
chemistry with this element (Fig. l), a chemistry which depends upon the ability of the two (or more)
metal atoms to interact with each other. The implications of this chemistry for the understanding of
oxidative addition processes 4i'6 in dinuclear and polynuclear complexes is the focus of this report.
A very well presented description of the recent organometallic chemistry of gold by Grohmann and
Schmidbaur should be consulted for more general information than is contained in this report. 51

2. GENERAL FEATURES OF T H E OXIDATIVE ADDITION P R O C E S S

Oxidative addition at a single metal centre is described as a one- or two-electron exchange between
the metal atom and the molecule being added. 3 The one-electron process is "radical" in character,
while the two electron exchange most often is described in terms of nucleophilic substitution, SN2.
In dinuclear compounds the distance between these metal atoms can influence the oxidative
addition chemistry. The metal atoms may be held close by bridging ligands or by other bonding
interactions. The specific electronic properties of both of the metal atoms, therefore, can influence
the observed chemistry. Widely separated metal atoms are expected to behave relatively inde-
pendently (Fig. 2), but if the metal atoms are close, factors related to the extent of metal-metal
interactions and the electronic properties of the metal atoms as adjusted by the ligands must be
considered.
 Metal metal bond formation in the oxidative addition to dinuclear gold(I) species

S£ngle Center
M M + A
2

Two Center

A -- M M ~A

Fig. 2. Oxidative addition to dinuclear complex. 5d

Goddard and Low 6 have discussed the role of electronic structure in oxidative addition. They
suggest that an electronic promotion occurs at the metal centre undergoing "oxidation". The
promotion is considered from a closed or pseudo-closed-shell ground state configuration to an
open-shell configuration, which can be associated with a (excited state) configuration suitable for
bonding to the molecule being added. In the case of the closed shell d l° complexes such as Au ~ or
Pt ° this open-shell configuration is d9s ]. Hence, the greater the energy separation between the d ~°
a n d d9s t configurations, the more difficult the oxidative addition process. Table 1 lists the closed-
shell to open-shell ( H O M O - L U M O ) energy separation 7 for ions of interest to this report. In the
G o d d a r d - L o w model, 6 excitation to the open-shell configuration, not oxidation (ionization), is the
key to understanding the reactivity.
Although there are obvious features in common between the oxidative addition studies described
in this report and studies involving open-shell ions such as Ir ~ or Pt H, the specific influence of
completely filled electronic levels at the metal atom is different enough from system to system that
electronic generalizations become less reliable. Hence, this report will focus on the oxidative addition
of closed-shell metal species, with one important exception on which calculations have been perfor-
med. 4~ For closed-shell d ]° metal atoms or ions, the experimentally observed pattern of closed-shell
to open-shell energy separation determined from spectroscopic data 7 parallels the oxidative addition
process. For the ions important to this report the energy separation pattern is: Hg"
> Ag ] >> Au ~ > Pd ° > Pt °. The greater the energy separation, the more difficult it is to achieve
oxidative addition. Conversely, the smaller the energy separation between the closed- and open-
shell configurations, the easier the addition. This concept is very similar to the idea of Chatt, ~
who stated that the stability of organometallic compounds closely follows their H O M O L U M O

Table 1. Promotion energies ("HOMO-LUMO gap

separations") and ionization potentials for some ions
important to oxidative addition reactions (eV)

HOMO-LUMO Ionization
Ion gap (eV)" potential (eV)

Cu I 2.715 20.292
Ag I 4.959 21.49
Au I 1.859 20.52
Pt° 0.744 9.00
Pd ° 0.814 8.337
T11 6.137 20.4
Pb" 7.488 15.03
Hg II 5.306 34.2

"The energy separation between the closed-shell

atomic configuration and the lowest open-shell con-
figuration.
4 J.P. Fackler Jr
separation. Changing the HOMO-LUMO separation by using different co-ligands at the metal
centre changes the reactivity of the complex, a concept widely utilized in organometallic syntheses.

3. OXIDATIVE ADDITION IN DINUCLEAR AND POLYMETALLIC SYSTEMS

With dimetallic and polymetallic systems, the excited-state energy as well as the ground-state
energy will be influenced by the close proximity of another metal atom. Spectroscopic evidence
suggests that metal-metal bond formation9 contributes to the description of the excited state with
some of these species. Obviously, metal-metal bond formation makes the "open-shell" excited state
more accessible relative to the case in which no metal-metal bond can form, for example, when the
metal atoms are well separated.
Electron-accepting metal centres or ligands adjacent to the metal atom undergoing the initial
attack during the oxidative addition can be expected to stabilize the HOMO or "closed-shell"
ground state through electron exchange. This increases the HOMO-LUMO separation, thereby
making oxidative addition less favourable. Similarly, cation charge and pi-bonding from adjacent
metal atoms or ligands also can be expected to increase the HOMO-LUMO separation, diminishing
the tendency for oxidative addition, relative to uncharged or electron-rich anionic complexes or
those complexes with strongly donating ligands.
Experimental differences are observed in the ease of small molecule oxidative addition to various
dinuclear gold(I) complexes having different charges or ligand atoms on the metal centres. For
example, with [Au2(diphos)2]2+, diphos = Ph2PCH2PPh2, a cationic complex with pi-accepting
phosphorus ligands, halogen addition does not occur, ~°even with very strong oxidants such as C12.
However, with the neutral complex [Auz(o-PC)2], o - P C = PhzP--C6H4,

containing the strongly basic phenyl ligands, iodine readily adds. u In both types of compound, the
Au-.. Au distance is ca 3.0/~. Several dinuclear gold complexes with C - - A u - - S and S--Au--S
coordination 12also exist with A u . . . Au separations of ca 3.0 A and are known to add halogens (see
below), but less readily than the ylide complexes of Fig. 1.
Accumulated data regarding the reactivity of dinuclear and polynuclear metal complexes is consistent
with the idea that neighbouring metal atoms and coordinated ligands influence the oxidative addition
process both positively and negatively.
Methyl iodide oxidative addition across two metal atoms with metal-metal bond formation was
first reported in 1975 by Schmidbaur 13a'~3bfor a dinuclear gold(I) ylide complex and shortly thereafter
by Gray 14 for the [Rh2(bridge)z] 2+, bridge = NCCHzCH2CN. X-ray structural results were not
easily obtained for either complex. The gold complex is photosensitive and easily decomposes into
the metal-metal bonded diiodide product. However, Basil successfully crystallized this complex,
which has the structure we reported 15 in 1982. Structures also have been reported for products
having CH3Br and CH3I across metal-metal Rh--Rh 16and Pd--Pd ~7bonds, but these adducts had
been obtained by protonation of methylene bridged A-frame intermediates.

4. OXIDATIVE ADDITION TO DINUCLEAR GOLD(I) COMPLEXES

In general, alkyl halide oxidative addition reactions that have been studied with dinuclear gold
ylide complexes follow the kinetic and thermodynamic patterns expected for SN2-type nucleophilic
 Metal-metal bond formation in the oxidative addition to dinuclear gold(I) species

--" ~"N - - - ~ / R
Au Au + RX ~ < /Au
< ~..-P
) #o!
o
x/ ~P ...... ,,

Equilibrium: CF3CH2I >> CH3CH2 I

Kinetics: PhCH2Br (120) >> CHsBr (20) >> (CHs)sSiCH2Br (I)

Fig. 3. Alkyl halide oxidative addition, thermodynamics and rates with relative rates in
parentheses.

reactions '8 summarized in Fig. 3. The Au ~centres have been established to be nucleophilic through
structural characterization of the SO2 adduct. ~9 The reactions with methyl halides are chemically
reversible in solution and also in the solid state.
Not only do dinuclear Au' ylide complexes undergo a two-electron oxidative addition with metal
metal bond formation, but oxidation by four electrons also can occur, producing products which
can be isolated and structurally characterized. 2° Since the four-electron oxidation proceeds through
a metal-metal bonded Au n intermediate, this metal-metal bond must be broken while producing
the Aum products. A number of these reactions have produced well characterized products (Fig.
4). We also have observed ligand exchange to occur at the Au Hcentres without oxidation. 2~However,
oxidative addition to the dinuclear Au H complexes often gives radical products. Except for the CH=
insertion reactions into the metal-metal bond using diazomethane and the known two-step addition
of dihalomethanes to the dinuclear ylide complexes, which also apparently involve a CH2 insertion, 5e
it is not known what role metal-metal bonding interactions play in influencing the course of these
reactions. Therefore, detailed consideration will not be given in this report to the four-electron

X
20e,38 X X
/"'~,U"' exchange s ubs titution
,~p~U,.
Br
|1 I X /,,ill I / I ,,ill%
P" ,,.... _ _ l 1 ,,,, ,1
xX.X k $nCl X
A ---/ N
~X
~Au/"
FF'(F
35 / ~ C d (C also
X NaCN, NaOAc
Fs)2
x2 ox i da t i on ll'""'PL?U~p .....~l

X ~ X
~/<%u., 3 ~ X 37
X CH ~p
~/-'A,.,_ + , ,....
. I1 ....,,
,....P , -'l ~ / p.
X " ~ ,x '\" _.iso /A~./ \
36, 20e X Au~/P-- x exchange X

Fig. 4. Reactions of dinuclear gold(II) complexes.

6 J.P. Fackler Jr
oxidative addition process, the radical oxidative additions or oxidative additions from dinuclear
Au H to Au IH species, although some dinuclear Au"/Au "t chemistry will be described.

5. D O E S T H E INITIAL OXIDATIVE ADDITION INVOLVE B O T H M E T A L CENTRES?

The oxidative addition scheme proposed for the dinuclear Au ~ complexes (Fig. 5) suggests that
metal-metal bonding promotes the formation of an ionic intermediate. While a cationic product of
this type has not been characterized structurally, a related species has been characterized by Uson,
Laguna and Laguna. 22a This dicationic species has a short, 3.6 A, metal-metal bond. Thus cationic
A u - - A u bonded intermediates are very reasonable intermediates in the dinuclear oxidative addition
process. Comparative structural data for the CH3CH2I and CF3CH2I adducts suggests ionization
of the I - in the ethyl adduct is more facile than in the case of the thermodynamically more stable
trifluoroethyl iodide adduct. 22b Furthermore, halide exchange at the Au II centres is known to be
rapid. 22c How certain are we that metal-metal bond formation occurs in the initial oxidation step?
After all, a mixed-valent AuI/AC" intermediate could be formed initially and then rapidly rearrange
to the observed products. More will written on this point.
The best evidence we have that nucleophilic attack by a Au ~ centre on the addend molecule
involves metal-metal bond formation originates from the structural results obtained with the SO:
adduct. 19 In addition to establishing the nucleophilicity of the Au I, which produces a pyramidal
geometry about the S atom, 39The Au ~. • • Au I distance shortens to 2.838 from 2.976 A. The donation
of electron density from gold to the SO2 is accompanied by increased metal-metal bonding. Although
formal "oxidation" does not occur with SO2, the process is similar to what is expected in a G o d d a r d -
Low6 oxidative addition, but with incomplete electron transfer to the ligand centres. There is an
overall two-electron deficiency for the formation of three sigma bonds along the S - - A u - - A u - - S
axis. (The SO2 contributes no electrons to the addition while each Au t atom contributes two electrons
to the axial sigma bonds.) Alternatively, it may be argued that the shortened gold distance has
resulted from the removal of repulsive electron density at the Au x centres by the SO2. Notably, the
Au ~ atoms in this complex are coordinated by four ligand atoms in an approximate plane, a rare
occurrence with Au ~. The author is aware of only three other examples, a pentanuclear gold complex
reported by Uson, 22 the SO2 adduct to the trinuclear [ A u - - - P t . . . A u ] complex described below 19
and a recently characterized tetranuclear complex, 23 in which [Au(TPA)3] +, TPA = 1,3,5-triaza-7-
phosphoraadamantane, coordinates through Au ~to [Au2 (i-MNT)2]2+, i-MNT = [S2CC(CN)2]2+.

/ I-

[-
~'" ! ~ / intermediate

.,Au ~
I/ ~ P""'m
product

Fig. 5. Anchimerically assisted nucleophilic addition.

 Metal metal bond formation in the oxidative addition to dinuclear gold(I) species
C1 tht 2+
I 1
[Ag(OClO3)tht]

l
-AgCI i k._
Cl I
tht

There is related evidence that metal-metal bonding accompanies the donation of electron density
to small molecules interacting with the Au ~atoms. Several years ago, Schmidbaur and his students -~4
recognized that a mixture of different dinuclear ylide complexes exchanged ligands slowly enough
that the various isomers could be separated on a column. This observation requires that A u - - C bond
rupture occur, a process likely to be influenced by either by intermolecular Au. •. Au interactions, or
by solvent effects, since ring opening would leave a Au ' centre coordinated only to one C atom. In
our effort to synthesize the dinuclear ylide complex of [(CHz)zP(CH3)C6Hs] to examine the question
of A u - - C bond lability, it was discovered'gb that the standard basic conditions for synthesis led to
the crystallization of only the trans isomer. This isomer rearranged in solution, slowly forming an
approximately 53 : 46 mixture of the trans and cis forms. The cis form has not been structurally
characterized, but is clearly identified in the N M R patterns obtained. Oxidative addition of halogens
or other oxidants leads to crystallization of trans dinuclear Au u products which do not undergo
further rearrangement. 25

R "P\ Au__/P'°', ~ ,,'"P\ Au__/P",,

trans tin

The trans to cis/trans rearrangement was found to be general acid catalysed. Strong protonic
acids such as HC1 are known to symmetrically cleave 26 the eight-membered ring, with deuterium
incorporation into the ylide using DC1. However, CD3COOD catalyses the isomerization without
introducing D into the complex. Since SO2, Ph3PAuC1 and other Lewis acids also catalyse the
isomerization, it was suggested 19b that rearrangement occurs via the formation of an adduct such
as the structurally characterized SO2 adduct with its shortened A u . . . Au interaction, an adduct of
a type similar to the initial electrophilic interaction suggested for small molecules undergoing
oxidative addition at the Au ~centre.

6. E V I D E N C E T H A T O X I D A T I V E A D D I T I O N D O E S N O T F I R S T F O R M A M I X E D -
V A L E N C E Aum/Au ! S P E C I E S

Although the SO2 studies are consistent with a nucleophilic attack by a Au j centre on the adduct,
which is assisted by metal-metal bond formation, it remained plausible that the addition occurs
first at one centre to form a Au 'n species, followed by a rapid rearrangement to the dinuclear Au u
product observed. Structural data for the addition of 12 to [Au(MTP)]2 clearly established that both
the homovalent and the mixed-valent species were formed with this halogen. 27 However, ligand
rearrangement also occurs causing the Au nt centre to have trans-AuC~_I: coordination. The dinuclear
M T P species with added C12 or Br2 crystallize a s A u 11 products, 2~ but the C~-[AulAum(MTP):CI2]
could be formed starting with the AunI(MTP)2C1)°a Thus, a synthesis of the mixed-valent ylide
complex with C1 or Br ligands seemed reasonable, especially if these materials were not intermediate
in the formation of the homovalent Au u products. Furthermore, Schmidbaur had previously
demonstrated that the dimethyl product is C,-{AutAum[(CH2)2PPh2]~Me2}, at least in solution, 2~
Uson et al. 3° had demonstrated that the dinuclear complex R2Au2[(/~-PPh2)2NH], R = C~Fs, was
oxidized to a metal-metal bonded Au H species, which then rearranged in polar solvents to a mixed-
valent Aum/Au I product, a rearrangement we also reported 4° for the dinuclear ylide complexes.
 J. P. Fackler Jr
~,Br

/\ \ .J
R N....I R - Ph

The synthesis of Cs-{AuIAuIn[//-(CH2)2PPh2]2Br2}, was accomplished 2°b'2°¢by oxidizing {AuII[fl-

(CHa)2PPh2]CN}2 with excess Br2 in CH2C12 or by reducing the trans,trans-tetrabromide with
AgCN in CH2C12. Both this material and the chloride analogue [Au... Au, 3.052(2) A] were
insufficiently soluble as the CH2C12 solvates to perform solution NMR studies of the rate of
rearrangement to the Aun/Au n product. If the material was heated in contact with the solvent, the
product formed from the resulting solution is largely the AUII/AuII species.
This data appears to mitigate strongly against a mixed-valent Aum/AuI species being formed first
in the oxidative addition process. However, this assumes that the initial oxidative addition product
is a mixed-valent species, in which the halide atoms are trans to each other on the A u nI centre. Since
dinuclear A u n l / A u In species had been synthesized and characterized, in which the halides (or sulfur-
containing ligands) were cis on both centres and also species cis on one centre and trans on the
other, 2°ethe possibility remained that oxidative addition involves cis addition at one centre followed
by rearrangement to the stable Aun/au n product. Schmidbaur had reported the formation of trans
asymmetric AuIll/Au~ cations from the reaction of {Au[#-CH2)PPh2]X}2 (X = Br, CI or I), with
neutral ylides, CH2 = PR3 (R3 = Me3, MePh2 or Ph3). These complexes had been characterized by
NMR and 197Au M6ssbauer spectroscopies. 32
The reaction of BrCN with Au2[~t-(CH2)2PPh2]2 leads to three products, as determined from the
1H NMR patterns and by crystallographic characterization of isolated products. The A u I / A u nl
dibromide product found (Fig. 6) in the cis form was isolated from the mixture of products after
dissolution in CH2C12 and layering with benzene or hexane, while being exposed to sunlight or a
UV sourceJ l Unfortunately, overexposure produces gold mirrors, but defining the conditions for
"overexposure" have not yet been achieved. The formation of the cis AuI/AunI product was
reproduced, however, and the material was characterized by X-ray crystallography. With regard to
the topic of this report, the cis adduct at the Au m centre does not undergo transformation into the

Fig. 6. Thermal ellipsoid drawing of the structure of the cis-Au I AuHI[#-(CH2)2PPh2]Br2.

 Metal-metal bond formation in the oxidative addition to dinuclear gold(I) species

symmetrical Au n material. Thus, cis oxidative addition at one centre followed by rearrangement
cannot be important to the oxidative addition process itself.
While oxidative addition of symmetrical oxidants invariably leads 5d to symmetrically ligated
(trans) metallocycles, {Au[#-(CH2)PPh2]X}2 (X = Br, C1, C N , 37 O O C P h , 42 NO333 and C6F521) and
metathesis can be used to produce new symmetrically ligated complexes (X = CF321), asymmetrically
ligated species also {Au[p-(CH2)PPh2]XY}2 have been synthesized from the oxidative addition of
alkyl halide reagents: X = Br, Y = Me, CH2Ph, CH2C(O)Ph, 43 CH2CN, CHC12; X = C1,
Y = CC13 ;36 X = I, Y = Me, ~5 CH2CH3, 44 CH2CF3, 44 CH2SiMe3, 5a CH2CI. 46 In fact, the kinetics of
the alkylhalide addition follows a pattern typically expected 5d for Sy2 processes. The addition
furthermore was shown to be reversible with the addition product stability greatly dependent 44 on
the presence of electron-withdrawing groups on the alkyl moiety.

7. R A D I C A L I N T E R M E D I A T E S

Nitroalkanes oxidatively add to [Au(ylide)]2 to produce N O 2 coordination and carbon-based

radical products. 33 While the initial step may be a non-radical oxidative addition for this system, as
suggested for the alkyl halides, followed by rapid homolytic A u - - C bond cleavage induced by the
strong trans-labilizing effect of the NO2, this reaction is sufficiently complicated that further study
is essential to determine what bearing it has, if any, on binuclear oxidative addition. Radical
coupling of the T H F solvent is known to occur. The addition of C H 3 N O 2 to the Au H species,
Au2(ylide)2(OBz)2, OBz = benzoate, causes insertion of CHNO2 into the A u - - A u bond. 33 Radical
processes also appear to be involved in the formation of the products in these systems.
Although strong evidence exists in many oxidative addition reactions 4~ that a one-electron first
step can occur in oxidative addition (electron transfer to the addend) to form a metal-based cation
radical, evidence for such radical intermediates with the dinuclear gold compounds appears limited
and is greatest in systems involving the addition of nitroalkanes, 33 disulfides tgb'47 or diselenides, 4~
sulfur 49 and the addition of strong oxidants, which have sterically blocked C centres such as 36 CC14
or centres which are only weakly aurophilic such as in benzoylperoxide. 42 While no Au~/Au"
radical intermediates have been characterized, nor have they been observed from ESR studies,
uncharacterized "blue" intermediates sometimes are observed. Evidence for radicals was found with
the CC14 addition, in which there was the formation of sufficient H C C I 3 in T H F to account for the
Au n and Au HI products isolated. However, even with CC14, a metal-metal bonded CI--Au(/~-
ylide)2Au--CC13 adduct could be isolated and structurally characterized. 36 Metal-metal interactions
also could promote an electron-transfer first step in the oxidative addition process.
The oxidative addition of small molecules to the dinuclear Au n species also can occur by one-
electron steps or a two-electron process. Structural evidence, 5¢ although weakened by a crys-
tallographic disorder, suggests that the second step in the formation of/~-methylene Au "~ derivatives

\
Br

formed from the addition of CH2Br 2 and its analogues to the dinuclear Au ~ complexes occurs by
insertion of CH2 into the A u - - A u bond. Diazomethane also adds across the A u - - A u bond in
dinuclear Au n species. 5°
In general, the formation of the dinuclear Au nl species (Fig. 4) must be accompanied by metal
metal bond rupture of Au u products. Direct oxidation to Aum species does not occur with weakly
oxidizing species such as alkyl monohalides, since the Au" centres are co,~siderably less nucleophilic
in the dinuclear Au u species than in the dinuclear Au I complexes, electron-transfer and radical
l0 J.P. Fackler Jr
intermediates are likely to be more important in the oxidation of Au n species than the Au ~
compounds. The H O M O in the Au H species is metal-metal bonding and metal-halide antibonding,
giving rise to a strong transannular influence of the alkyl group on the metal-halide distance. This
lengthening of the Au-halide bond compared with similar bonds in mononuclear sigma-bonded
compounds has been described as an amplified structural trans influence? d
Although the dinuclear Aum complexes rapidly react with the dinuclear Au ~ylide dimers to form
Au n products, only symmetrical Au ~' products have been isolated to date by this route. Furthermore,
kinetic and mechanistic studies designed to determine whether this reaction follows atom-transfer
or electron-transfer dynamics have not been performed. The lability of the AuH-halide bond in the
presence of the dinuclear Au ~ species may impede the development of meaningful mechanistic
studies.

8. OXIDATIVE A D D I T I O N O B S E R V A T I O N S W I T H O T H E R DINUCLEAR GOLD(I)

COMPLEXES

The fact that dinuclear diphos complexes of Au I do not oxidatively add small molecules prompted
us to examine the possibility of addition to other dinuclear Au I species. Isolated, characterized
products have been obtained by us and others for the species listed in Fig. 7. As stated above, the
iodide products undergo rearrangement to mixtures which contain AuI/Au m products. The [Au2(i-
MNT)zX2] 2- species are compounds which slowly rearrange 5~in solution to Aum and Au ~products.
This rearrangement has been studied kinetically and is found to be first order in added halide. Thus,
the presence of free halide nucleophiles presumably impacts upon the product distributions found
in the oxidative additions to dinuclear Au I species, such as reactions observed with Au2(MTP)2 and
even the ylide complexes. Qualitatively, rearrangement to Aul/Au m products appears to be associ-
ated with the electrophilic nature of the Au ~ centres in the oxidative addition product. With
P - - A u - - C , S - - A u - - C or S - - A u - - S coordination at the Au n centres, halide exchange is facile
and the metal centres are sufficiently electrophilic so that rearrangements are found. Burmeister
suggested 52 that even the well-known Au2(dtc)2, dtc = dialkyldithiocarbamate, forms a symmetric
Au H product when oxidized with halogens. However, the material was found to be too unstable to
isolate at room temperature. The anionic charge associated with the i-MNT complex, in which the
Au ~ product has a nearly identical coordination structure to that of the Au I dithiocarbamate,
appears to give the Au H species, [Au2(i-MNT)zX2] 2-, greatly increased stability. The fact that the
stability of these species in solution changes in the order C1- > Br- > I- follows closely the
increased nucleophilicity of any halide freed by ionization. This observation may account for some
of the difficulty our group had initially ~3in reproducing Schmidbaur's observation of CH3I addition
to the ylide complex, although the primary problem was the sensitivity of the complex to UV light. 5d

9. I M P L I C A T I O N S OF T H E G O D D A R D - L O W OXIDATIVE ADDITION C O N C E P T
T O T H E DINUCLEAR GOLD(I) C H E M I S T R Y

The oxidative addition chemistry described above follows nicely the G o d d a r d - L o w concepts.
Basic ligands attached to the Au ~ centres enhance the ease of closed-shell to open-shell formation.
The open-shell configuration on the Au I centre to which the small molecule is initially added involves
a d-orbital perpendicular to the axis of ligand coordination to the Au ~and directed, at least partially,
toward the adjacent Au ~ centre. As long as this distance is around 3.0 A or less, an A u - - A u bond
can form, leaving the second metal atom "open". With alkyl halides, nucleophilic attack by the Au ~
on the C atom with metal-metal bond formation and heterolytic C-halide bond rupture (Fig. 5)
leaves the second gold centre coordinately unsaturated and the overall charge of the complex
cationic. Hence, the reaction pattern is the same as observed for oxidative addition to square planar
complexes, but gives a product with the addition across the A u - - A u bond. The fact that the cationic
[Auz(diphos)2] 2+ complexes do not oxidatively add small molecules or otherwise easily oxidize
appears directly related to the apparent increase in the energy required to obtain the open-shell
configuration with phosphine ligand coordination and the positive charge on the complex.
The presence of another metal ion centre such as Hg 2+ or T1+ adjacent to the Au ~ in dinuclear
M T P complexes also prevents the oxidative addition. 53 While the charge may be important with
 Metal-metal bond formation in the oxidative addition to dinuclear gold(I) species ll

X Au Au X

R R
I Au Au I

I
H
! ~ 2 P
'Nph Ph

3 Ph-- I i~.Ph
X Au' Au X

R
I R
I
jP~
2-

,
X
x Aul Au
Au -, S P~!
4

S
I
Au
%
x 5
Fig. 7. General classes of structurally characterized dinuclear An u compounds : 15m [Au2(I~-
(Ctt2)2PR2)2X2] ; 2 ~ [Au2(o-PC)212] ; 33o R2Au.[I~-PPh2)2NH] : 4'-~b[Au2(MTP)2X~] • 5 s~ [Au:(i-
MNT)2X~]-" • X is generally a halide but also may be a variety of other anions.

Hg-7 4 , the n e i g h b o u r i n g g r o u p influence is m o s t likely to be the failure o f the two a d j a c e n t m e t a l

a t o m s to be able to form a g o o d electron p a i r b o n d .

4-

Hg Au
1 PF 6- or BPh 4-
~p1 S
/\
Yet, with all o f the studies p e r f o r m e d to d a t e with d i n u c l e a r A u ~ complexes, s o m e u n c e r t a i n t y
still r e m a i n s r e g a r d i n g the specific role the a d j a c e n t metal a t o m p l a y s in electronically influencing
the o x i d a t i v e a d d i t i o n . W h i l e the G o d d a r d - - L o w c o n c e p t a p p e a r s to explain the results o b s e r v e d
12 J.P. Fackler Jr
for dinuclear oxidative addition, a clearer understanding of the impact of the electronic properties
of the adjacent metal center comes from studies of the chemistry of linear trinuclear species.

10. OXIDATIVE ADDITION TO LINEAR TRINUCLEAR SPECIES

Direct evidence for a positive electronic influence of a neighbouring metal atom on the oxidative
addition process, with a resultant metal-metal bond formation, can be observed in the chemistry of
linear trimetallic species. The process that leads to "terminal addition" (Fig. 8) is a typical two-
electron oxidative addition. This product is the expected product as long as the metal atom in the
middle of the linear array, M, allows addition to take place. The two-electron oxidative addition
which produces the four sigma bonds, the "trans addition", cannot occur with metal-metal bond
formation unless M contributes electrons and orbitals to the process. Four sigma bonds cannot
form from a two-electron oxidative addition event.
The Goddard-Low concept of oxidative addition pinpoints the metal atoms, M, for which the
trans addition might become possible. Assuming that the unoxidized species has M in planar
coordination, a filled orbital near the HOMO and an empty orbital near the LUMO in energy must
be found which can be involved in the bonding. To form metal-metal bonds, these orbitals must be
directed largely along the metal-metal axis. Open-shell formation at M' can induce bonding to M,
but it also must promote an electron into an empty orbital at M. This orbital becomes an open-
shell orbital which allows bonding to the other M'. Consequently, A 2 adds across the three-metal-
atom array. Should M not have available orbitals for bonding to M' nor two electrons to contribute
to the bonding process, single centre oxidative addition might occur providing the neighbouring
metal atom did not inhibit addition totally as observed in many dinuclear systems.
Single-centre oxidative addition has been observed with the trinuclear pyrazolate (pyra) species
tris-(/~-3,5-triphenylpyrazolato)trigold(I). When the planar complex [Au~(pyra)]3 is oxidized with
halogens or even with aqua regia the mixed-valent product [Au"~CIEAUE(I)(pyra)3)] is obtained,
which has been structurally characterized (Fig. 9). The distance between gold atoms is ca 3.3 A in
the unoxidized and oxidized materials.
The MTP ligand furnished us with an opportunity to synthesize linear trinuclear species in which
the oxidative addition process could be testedd4 By reacting [PPN][Au(MTP)2] with K2PtCI4 the
product trans-[Au"(p-MTP)2Pt(#-MTP)2Au"]C12 was obtained and studied structurally (Fig. 10).
The unoxidized precursor [Au~(/~-MTP)2Pt(#-MTP)2Au l] was formed from [PPN][Au(MTP)2] by
reaction with cis-PtC12(SEt2)2. Oxidation with halogens or with PhIC12 cleanly forms the A u n
product, which can be reduced back to the Au ~material with LiCH3. Oxidation shortens the Au--Pt
distance from 3.03 to 2.66 A. In these complexes the Pt atom is planar and four-coordinate to the
S atoms of the bridging MTP ligands. Aside from the formation of the terminal metal-halide bonds
and the shortening of the Au--Pt distance, the geometric changes found upon oxidation of the
complex are small.

+A 2

terminal addition

trans addition
Fig. 8. Oxidativeadditiontolineartrinuclearspecies.
 Metal-metal bond formation in the oxidative addition to dinuclear gold(l) species 13
(non-linear arrangement}

- " -

N N Aqua Regla
\ I /i \ /
Au /Au Au Au
N N \ N
/
N

Au...Au 3.3 A C1
Fig. 9. Oxidation of tris-(#-3,5-triphenylpyrazolato)trigold(I) with aqua reyia.

\p.++" ] ..,
,.-" ~ s s~P~
I..,
# ..-"
Au Pt Au
Abbrev.[Au...Pt...Au]
41
~ p ~ S J

X2, (X - Cl, Br, I)

/ ~
/ "V-'-,. - CI, Br, I)

\,.++" ~..,

Au Pb Au Decomposition X -- Au-------- p t Au~ X

/|
p halogen
/ "-..,'-".., oxidation to
Au(I),Au(III),Pb(II) Au-Pt 2.6 A
Fig. 10. Linear trinuclear [Au... Pt... Au] and [Au-.. Pb... Au] complexes with the ligand
MTP.

As in the dinuclear gold ylide complexes, SO2(g) also adds 19ato the [Au~0t-MTP)2Pt(/~-MTP)2Au~].
The shortening of the A u - - P t distance to 2.868 A and the pyramidal geometry about the coordinated
S atom bonded to the Au entirely parallels the observations made with the SO2 addition to the
dinuclear ylide complex. Thus, the nucleophilic interaction of the gold centres with the SO2 leads to
partial "oxidation" of the complex, with full oxidative addition occurring upon halogen addition.
Fenske-Hall calculations 4i show that the H O M O in the linear trinuclear complex [Au. - - Pt. • • Au]
is antibonding with respect to the metal-metal interaction along the linear metal axis. Oxidation
results in the formation of a bonding H O M O along this axis. While it is convenient to describe the
gold atoms as the atoms being oxidized, the correct description is that a [ A u - - P t - - A u ] 2+ moiety
bridged by the MTP and coordinated to the halides is formed.
14 J.P. Fackler Jr

A G o d d a r d - L o w description of this trinuclear oxidative addition process implies that the closed-
shell d 1° Au I centre becomes an open-shell species upon interaction with the oxidant and induces an
"excitation" of the Pt H in the middle of the complex. The unoxidized complex has a typical, well-
studied PtS4 coordination with a H O M O involving significant dz2 character and a L U M O with
substantial Pz character. The filled d,2 orbital falls along the metal-metal axis. Promotion of an
electron from this orbital to the p, orbital produces an "open-shell" configuration, which induces
the formation of the open-shell configuration for the second gold atom. Electron pair bonds are
formed between the gold and platinum atoms.
The G o d d a r d - L o w description of the oxidative addition process for the trinuclear species suggests
that the metal atom in the middle of the complex must have electrons to contribute to the bonding
and low-lying "open-shell" excited state. Several metal ions in addition to Pt n are reasonable
candidates such as Ir I or Pd H, but to date trinuclear M T P species with these ions as the metal in the
middle have not been characterized. However, Pb" in the complex [AuI(/~-MTP)2Pb(/~-MTP)zAu I]
does occupy essentially the same coordination position as Pt n, Fig. 10. 55 The geometry is not
rigorously square planar about the Pb n as it is with the Pt n, but the tetrahedral distortion is very
small. The Au I . . . Pb H distance is about the same as Au ~--. Pt n distance, 3.0 A. Oxidation of this
complex with PhICI2 or halogens leads to decomposition. Stoichiometric studies with PhIC12 indicate
that the oxidation produces approximately equal molar quantities of Au l, Aum and Pb" species.
There appears to be no stability to any oxidized trinuclear product.
Since the four coordinate Pb H in the centre of the trinuclear ( A u . . . P b . • • Au) complex contains
no low-lying empty orbitals, promotion from the s 2 configuration of the ion must be into antibonding
P b - - S orbitals. In fact, F e n s k ~ H a l l calculations 55 indicate that the H O M O in this system is largely
Pb(6S) in character, with bonding and antibonding contributions from the Au atoms. The S H O M O
is bonding in character, making oxidation considerably more difficult than with the Pt complex
where the H O M O is antibonding. Promotion to the L U M O produces no net metal metal bonding
as apparently occurs with [Au. • • P t . . • Au] (Fig. 11).
The chemistry of a third linear trinuclear M T P complex 4~ further relates to the G o d d a r ~ L o w
model of oxidative addition. This cation [Hg2Pt(MTP)4] 2+ (Fig. 12) is exactly isoelectronic with the
[Au • • • P t ' . - Au] species. However, it undergoes no oxidation chemistry with mild halogenation. Various
salts of the cation have been characterized, but chemical oxidative addition has not been achieved in
any case. In this system which is structurally similar to the other complexes, the H O M O has no H g - - P t
character and is largely associated with the P t - - S coordination. The L U M O does have P t - - H g bonding
associated with it. However, promotion of the closed-shell Hg 2+ to its open-shell configuration is very
difficult energetically. It appears to be a "dead" system to oxidative addition.

11. S U M M A R Y

The oxidation or attempted oxidation by small-molecule oxidants of the linear [Au. • - P t - . • Au],
[ A u . . - P b . . . Au] and [ H g - - . P t . . - Hg] 2+ require us to acknowledge that neighbouring-atom elec-
tronic features can both inhibit and promote the oxidative addition process. A similar type of
electronic influence appears prevalent in the oxidative addition to dinuclear Au I complexes and
probably exists whenever the G o d d a r d - L o w concept of oxidative addition can involve both metal
atoms in the process. Metal-metal bond formation accompanying the oxidative addition stabilizes
intermediates which lead to the formation of products in which the addend adds across the metal
metal bond(s). The promotion of the oxidative addition will depend on the ease of closed-shell to
open-shell promotion of the neighbouring atom as well as the atom to which the adduct initially
interacts. Such behaviour presumably exists in m a n y systems wherein bimetallic heterogeneous
catalysis is more effective than in the monometallic system.

Acknowledyements~The author thanks the large number of students and postdoctorals who have contributed
to the studies described in this report. Their names are in the references. Three postdoctoral colleagues stand
out for their special contributions, H. H. Murray, III, Suning Wang and Richard J. Staples. The National
Science Foundation and The Welch Foundation made our studies possible. The author also thanks the Penguin
Foundation for support with a Wilhelm Manchot Research Professorship at the Technical University of
Munich and to numerous excellent discussions with Professor Hubert Schmidbaur of that institution and
Professor F. A. Cotton and Michael B. Hall of Texas A&M University.
 Metal-metal bond formation in the oxidative addition to dinuclear gold(l) species 15
Au21~(N'rP)4X2
Xt Au Pt Au. X2

Pz 5dz2+ 6s 5dz2 5dz2 + 6s Pz

XI (~Au Pt ~ _ Xz

HOMO
Pz 5dz2 + 6s 6Pz 5d~2 + 6s Pz
+ 6pz + 6pz

Au2Pt(MTP)4

Au I Pt Au2
LUMO
1.6 eV
27.7% 6pz 29.3% 6Pz 27.7% 6 Pz
H/L Gap -- 7.79 cV

-6.12 eV
9.2% 5~2 27.6% 5clz~ 9.2% 5dz2
+10.1% 6s +3.4%6s +10.1% 6s
Fig. 11. Qualitative HOMO-LUMO representation of Au2Pt(MTP)4 and Au2Pt(MTPLX> ~7

\ "'" N ,""" ~" 2+

[-"'-s pt2+
(,,"-s I ? "~/ x.
.""
Hg( I I ) ~ Hg Pt Hg

,
/ "-../%
Ig..Pt 3.IA
Fig. 12. Synthesis and structure of the cation [Hg2Pt(MTP)4]2+, which is ;soelectronic with
[Au...Pt...Au].
16 J. P. Fackler Jr
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