Journal of Molecular Structure: THEOCHEM 957 (2010) 2125

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Journal of Molecular Structure: THEOCHEM

journal homepage: www.elsevier.com/locate/theochem

Theoretical study of weak CC double bond coordination in a gold (I) catalyst

precursor
Mhamed Touil a, Benjamin Bechem b, A. Stephen K. Hashmi b, Bernd Engels c, Mohammad A. Omary d,*,
Hassan Raba a,**
a

Chemistry Dept., ESCTM, Ibn Tofail University, P.O. Box 133, Kenitra 14000, Morocco
Institut fr Organische Chemie, Universitt Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany
Institut fr Organische Chemie, Am Hubland, 97074 Wrzburg, Germany
d
University of North Texas, Department of Chemistry, 1155 Union Circle #305070 Denton, TX 76203-5017, USA
b
c

a r t i c l e

i n f o

Article history:
Received 18 January 2010
Received in revised form 29 June 2010
Accepted 29 June 2010
Available online 6 July 2010
Keywords:
Gold catalyst precursor
DFT
Ab initio
Dispersion
Correlation effects

a b s t r a c t
MP2, CCSD and DFT/B3LYP modelling were performed to gain insight into C@CAu interaction in the gold
precursor [(biphenyl-NMe2)Ph2PAuCl], A. Prior to this work, the existence of C@C coordination to the gold
(I) center as well as the nature of this precursor structure in the phenol synthesis have remained uncertain. To determine the nature of the bonding in the structure of pre-catalyst A, we carried out different
optimizations at different levels of theory. DFT results revealed weak AuC@C bond in models of A, longer
than the experimental X-ray bond length, while MP2 and CCSD attained higher accuracy. We also examined other congurations of the Au(I) center in phenol synthesis by computing several hypothetical neutral and cationic complex models. Four structures of related gold model complexes were optimized by
several methods. These computations suggest that the cationic pre-catalyst [(biphenyl)PH2Au]+ model
leads to a dissymmetric pC@C coordination and exhibits greater reactivity than that in the neutral [(biphenyl)PH2AuCl] model. The cationic complex was found to be more favorable than the neutral model from a
thermodynamic point of view (computed DG). Therefore, we suggest a possible equilibrium in situ
between the cationic and neutral forms. We also have carried out geometry optimization for the simplied cationic model [benzene-Au-PH3]+ in order to provide a more accurate assessment of the bond
energy and coordination sphere involving the g2-olenAu(I) moiety.
2010 Elsevier B.V. All rights reserved.

1. Introduction
During the last decade, homogeneous transition metal catalysis
has constituted an important eld of industrial chemistry [13].
Gold catalysis underwent an impressive development and became
an important tool in organic synthesis and offers new region-selectivity possibilities [48]. Considerable works were focused on a
gold precursor in fundamental and applied research [2]. Remarkable properties of these catalysts were used in the catalytic reactions: e.g. phenol formation. Gold (I) catalysts have been shown
to be particularly active for the cyclization of 1,5-enynes [1]. These
catalysts also promoted a variety of reactions for 1,5-enynes particularly in an Alder-ene type product showing a selective transformation of furan to highly substituted phenols [2].
Indeed, an increasing number of papers concerning the use of
the pre-catalyst gold or platinum in the catalytic systems [59].
It is important to notice for many catalysis reactions, there exists
* Corresponding author. Tel.: +1 940 565 2443; fax: +1 940 565 4318.
** Corresponding author. Tel.: +212 537 375 506.
E-mail addresses: omary@unt.edu (M.A. Omary), hrabaa@yahoo.com (H. Raba).
0166-1280/$ - see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.theochem.2010.06.030

no direct experimental proof for most of the intermediates shown

in the mechanistic proposals. However, these assumed intermediates help recognize the often complicated substrate/product relationships and similarities between reactions. Therefore, in the
intermediate of a catalytic reaction, a generalized gold complex
fragment [Au] is used to symbolize the unknown active species.
In order to predict the gold fragment structure [6,7b,9], theory can
help by assessing reasonable predictions on metal conguration
and structure. We present here a computational study for one of
the interesting gold reactions in phenol synthesis catalyzed by
[(biphenyl-NMe2)Ph2PAuCl] (A), which potentially exhibits weak
olen coordination to Au(I) that is relevant in experimental studies
by the Hashmi and Echavarren groups [10a,b,11,12].
The validity of genuine C@C coordination to the gold (I) center
in ML3 or ML2 catalyst precursor complexes remains uncertain,
so does the nature of the precursor structure involved in the phenol formation. Therefore, at rst goal, we carried out different
calculations on ML3 complexes via quantum mechanical computations at the DFT (B3LYP), CCSD and MP2 levels of theory in order to
make an estimation of the strength of the g2 C@CAu bond in the
gold (I) complex [(biphenyl-NMe2)Ph2PAuCl] (A). Secondly, other

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M. Touil et al. / Journal of Molecular Structure: THEOCHEM 957 (2010) 2125

hypothetical cationic models with ML2 structure were investigated

in this article to probe the involvement of the cationic gold precatalyst in the phenol formation, including estimation of the Gibbs
free energy (DG).

2. Computational methods
All molecular calculations were performed with the Gaussian
03 series of programs [13]. The geometries of all molecules were
optimized by applying density functional theory (DFT) using the
B3LYP functional [14]. The basis set was the LANL2DZ relativistic
pseudo-potential (ECP) for gold [15] and (6-311G++ (d,p)) was
used for C, O, N, Cl and P. Harmonic frequencies were calculated
for each complex model (neutral or cationic) to characterize the
stationary points. The geometry optimizations were performed
for the singlet spin state without constraint of symmetry. All stationary points were characterized as minima (no imaginary frequencies) by a Hessian calculation.
For a more accurate assessment of bond formation, other related methods including MP2 [16] and coupled cluster single and
double excitation (CCSD) [17] which are usually more accurate
for the resolution of the dispersion effect, were also used. In both
methods, we keep the same the basis set quoted above (6311G++ (d,p)) for C, O, N, Cl and P and the LANL2DZ relativistic
pseudo-potential (ECP) [15] for gold. Standard analysis through
NBO/MP2 (Natural Bond Orbital) was performed in certain models
[1322].

3. Results and discussion

3.1. Molecular and electronic structure of [(biphenyl-NMe2)Ph2PAuCl]
Fig. 1 shows the reaction investigated in this work, which is one
of the interesting gold reactions in phenol synthesis catalyzed by
[(biphenyl-NMe2)Ph2PAuCl] (A). The structure of (A), labeled [Au]
in Fig. 1, adopts a weak C@Cgold (I) bond [10a,10b,11,12]. Fig. 2
shows one portion of the X-ray structure of (A).
The relevant distances and angles in (A) are listed in Table 1. We
also observe that the torsion angles of ClPAuC1 and C1C2C3
C4 are slightly bented and respectively, equal to 164.7 and
110.1. By analyzing these data, the AuC3 and AuC4 bonds
are much longer than the usual bond AuC distances in standard
goldolen complexes (2.132.21 ) [9b]. In addition, the strength
of the presumed bonds AuC3 and AuC4 testify a weak interaction
goldligand. Interestingly, the AuP and AuC bonds are also elongated according to the dispersion effect. However, ClAuP angles
are so far not quasi-linear and this probably comes from the distortion imposed by the biphenyl ligand coordination or the packing
effect [12].

Fig. 2. X-ray structure of [(biphenyl-NMe2)Ph2PAuCl] (A) [10a]. Green ball: Cl;

Yellow = Au; Orange = P; Gray = C, Blue = N and White = H. (For interpretation of the
references to colour in this gure legend, the reader is referred to the web version of
this article.)

Table 1
Distances and angles from X-ray crystallographic data of [(biphenyl-NMe2)Ph2PAuCl]
(A).
Bond lengths ()

Bond angles ()

Torsion angles ()

Au1 P1 2.233(6)
Au1 Cl 2.288(6)
P1 C1 1.794(9)
P1 C31 1.838(8)
P1 C21 1.844(2)
C1 C2 1.377(3)
C1 N5 1.387(2)
C2 C3 1.396(3)
C3 C4 1.364(3)
C5 N5 1.369(3)
Au C2 3.743(3)
Au C4 3.192(3)
Au C3 3.167(4)

P1 Au1 Cl 176.3(7)
C1 P1 C31 103.7(9)
C1 P1 C21 107.2(9)
C31 P1 C21 106.9(9)
C1 P1 Au1 115.4(6)
C31 P1 Au1 112.2(6)
C21 P1 Au1 110.8(6)
C2 C1 N5 106.9(7)
C2 C1 P1 127.5(2)
C1 C2 C3 108.4(2)
C4 C3 C2 107.3(2)
C3 C4 N5 108.8(2)

ClP1AuC1C1 164.7(1)
ClP1AuC1C3 134.8(2)
ClP1AuC1C2 130.2(1)
ClP1AuC1C1 110.1(2)
C1C2C3C4 110.1(2)

In this section, our theoretical study is focused in the electronic

structure of [(biphenyl-NMe2)Ph2PAuCl] (A), using at rst the density functional theory (DFT) calculation. There are several interesting conclusions that emerge from the optimized structure of (A)
(see Fig. 3) and summarized in Table 2.
Thus, at B3LYP/(6-311G++(d,p)) level, (A) converges with a
weak CC double bond coordinated to Au(I) with AuC3 and Au
C4 bond lengths equal to 3.18 and 3.23 respectively but seems
much longer than the values seen in X-ray data (3.16 vs. 3.19 ,
respectively) (for comparison see top and fortieth row of Table 2)
[10]. We observe also a strengthen of AuP and AuCl equal to
2.29 and 2.26 , respectively. The PAuCl angle is equal to
174.4 closer to 176.3 founded experimentally. The tetrahedral
phosphor preserves a standard coordination with a little distortion.

R1
R

R2

[Au], 5 mol %
O

AgBF4, 5 mol %
DCM

R1
O

OH

Fig. 1. Schematic reaction of phenol formation using [(biphenyl-NMe2)Ph2PAuCl] as precursor (A) [Au].

M. Touil et al. / Journal of Molecular Structure: THEOCHEM 957 (2010) 2125

Au

C1

So, to get insight into the electronic structure of (A), HOMO

LUMO (highest and lowest molecular orbitals) contours of the
KohnSham [20] were investigated (see Fig. 4). The contour of
the HOMO demonstrates expecting weak pCC coordination to
dx2y2 gold orbital (small character) (top). As consequence, a small
overlapping <pC@C/dx2y2> = 0.10 occurs and may explain the quasi-longer AuC@C bond even at long distance. Meanwhile, the existence of the small p orbital gold interaction can also overlap
slightly via a feedback effect from metal to ligand as seen by the
shape of the LUMO (bottom of Fig. 4).

Cl

C4
C2

23

C3
C5
(Me)2N

3.2. Electronic structure of [biphenyl-PH2AuCl]

Fig. 3. Schematic labeling atoms in the [(biphenyl-NMe2)Ph2PAuCl] (A).

Table 2
Comparison of calculated metrics () and angles () for optimized isolated catalyst (A)
with different basis and theory levels.
Method/basis (Au)/atoms:CNOPCl

AuC3

AuC4

AuCl

AuP

PAuCl

B3LYP/6-311g++(d,p)
B3LYP/LANL2DZ/6-311g++(d,p)
MP2/LANL2DZ/6-311g++(d,p)
X-ray
Average crystallgraphic (CSD)

3.18
3.19
3.14
3.16
3.14

3.23
3.18
3.17
3.19
3.16

2.29
2.28
2.26
2.28
2.27

2.26
2.25
2.24
2.23
2.24

174.4
176.2
175.1
176.3
177.5

The point is that the gold endorses in this case a quasi-linear coordination of gold atom with a special hybridization (spd). Obviously,
the Au(I) is electron rich and C@C bonds could not make an agnostic bonds in this case, but it can generate a weak double CC bonding
at long distance via a large delocalization of p system. Moreover,
this C@C bonding is predicted to have a small overlap with gold. Indeed, the formal bond C3@C4 is notably imposed by the cyclization
of the biphenyl towards gold (I) center. The weak CC double bond
coordination to the central is also due to the higher polarization of
p system.
To obtain more thorough insights into this weak C@C coordination to gold (I) in (A), we carried out additional calculations with
different theoretical treatments [10]. As shown in Table 2 (second
row), for example, the use of LANL2DZ gives a shorter AuC3 bond
(3.19 ) than the one obtained using 6-311G++(d,p)) basis. Also
MP2/LANL2DZ gives rise to a slight decrease in metalligand distances vs. B3LYP/LANL2DZ, for example attaining (2.26 vs. 2.28 )
and (2.24 vs. 2.26 ) for AuP and AuCl bonds, respectively. Effectively, we observe a decreases of AuC3 and AuC4 bonds (3.14
and 3.19 ). The PAuCl and ClPAu average angles are equal
to 175.1 and 176.2, respectively, for MP2 and B3LYP/LANL2DZ
leading to a non-linear gold (I) structure but similar to the (Cl
AuP) angle founded experimentally [10a]. The weak CC bonding
in gold (I) coordination even at long distance generates a delocalized p around the metal and explains the non negligible C@C interaction seen in (A).
For comparison, we selected via Cambridge structural database
(CSD) [10b], similar structure of (A) (see bottom of Table 2 (fth
row). An average of bond lengths and angles of different complexes
belonging to the gold (I) class are compiled from Ref. [10b]. For
clarity in the text, we listed the most implied bonds and angles
in the bonding coordination of CC double bond coordinated to gold
(I) for (A) such as AuCi (i = 3, 4) (3.14 and 3.16 , respectively),
AuCl = 2.27 , AuP = 2.24 , and angle PAuCl = 177.5. An
analysis of these AuC bonds (Table 2 row 5), shows no large deviation upon ligand changes that are commensurate with the sample
standard deviations seen in (A). However, the angles are subjected
to an enhancing related to the package effect.

Indeed, to complete the above investigation, we carried out a

third investigation concerning the p dispersion effect on the hypothetical model [biphenyl-PH2AuCl] (B). In this model, we substitute
the two phenyl groups in (A) by two hydrogen atoms without varying other ligands (Fig. 5). Then, different optimization of (B) was
undertaken at different levels of theory, including B3LYP, MP2
and CCSD, and summarized in Table 3. Consequently, the CCSD calculation with its good correlation, on (B) converges on shortest Au
C3 and AuC4 bond distances equal to 3.13 and 3.17 , respectively.
The AuC3 and AuC4 bonds remain signicantly longer than the
standard AuC bond (2.22 ) seen in the bonding goldolen complex [9b,19], hence suggesting weak C@C activation by gold. Moreover, the use of LANL2DZ (third row in Table 3) gives an
underestimated AuC bond equal to 3.20 vs. 3.16 as founded in
MP2 (rst row of Table 3). The PAuCl average angles remains
equal to 177.1, 176.5 and 175.2 for MP2, CCSD and LANL2DZ calculations, respectively, and assesses a non-linear bonding ClAuP.

Fig. 4. Contour plots of the KohnSham HOMO (top) and LUMO (bottom) orbitals of
[(biphenyl-NMe2)Ph2PAuCl] based on DFT computations. Green ball: Cl; Yellow = Au; Orange = P; Gray = C, Blue = N and White = H. (For interpretation of the
references to colour in this gure legend, the reader is referred to the web version of
this article.)

24

M. Touil et al. / Journal of Molecular Structure: THEOCHEM 957 (2010) 2125

Table 4
Cationic optimization at different level of computation in [(biphenyl)PH2Au]+ (C).

MP2/LANL2DZ/6-311g++(d,p)
B3LYP/LANL2DZ/6-311g++(d,p)
CCSD

Fig. 5. Sketch of the second optimized model [(biphenyl)PH2AuCl] (B). Green ball:
Cl; Yellow = Au; Orange = P; Gray = C, Blue = N and White = H. (For interpretation of
the references to colour in this gure legend, the reader is referred to the web
version of this article.)

Table 3
Comparison of calculated metrics () for isolated catalyst [(biphenyl)PH2AuCl] (B)
optimized with different methods and basis.

MP2/LANL2DZ/6-311g++(d,p)
CCSD
B3LYP/LANL2DZ/6311g++(d,p)

AuC3

AuC4

AuC5

AuCl

AuP

PAuCl

3.16
3.13
3.20

3.19
3.17
3.27

3.58
3.66
3.12

2.28
2.35
2.41

2.23
2.32
2.42

177.1
176.5
175.2

Thus, by comparing these three correlative methods, CCSD gives

the shortest AuC bonds.
As conclusion, the two computed calculation (CCDS) and (MP2)
exhibits the same tendency and accuracy in terms of AuC bonds
better than DFT and lead to a dissymmetric g2 C@CAu bonding
in the gold complex. However, the pre-catalyst ML3 seems saturated electronically to give more reactivity in the catalytic reaction
and therefore, we propose a cationic gold (I) precursor, which has
more activity species and gives more efciency for the main reaction depicted in Fig. 1.
3.3. Cationic gold [(biphenyl)PH2Au(I)]+ model
Our interest in the CC double bond coordination in (A) led us to
study theoretically other related hypothetic gold precursor ML3 in
their cationic form. In this model, we remove in situ the chlorine
ligand in [(biphenyl)PH2AuCl] (B) as quoted in the reaction below
and built a cationic gold pre-catalyst [(biphenyl)PH2Au]+ (C) in order to diminish the huge polarization surrounded the gold.

AuC3

AuC4

AuC1

AuC2

AuC5

AuP

2.48
2.63
2.40

2.55
2.49
2.51

3.21
3.38
3.29

3.42
3.57
3.38

3.36
3.34
3.30

2.34
2.35
2.33

row) but shorter than 2.63/2.49 at DFT/LANL2DZ level (second

row) (see Table 4). In (C), we observe again that MP2 gives higher
accuracy than DFT in terms of AuC bond length.
As consequence of the above results, the short AuC distances
are due to the suppression of the chloro ligand involving direct
decreases of polarizability of gold in the cationic metal center.
Therefore, this coordination was furthermore initialized by the
electrophilic gold (I) complex and should be considered as a
central step of reaction in the phenol formation [1].
By using another bonding analysis approach, NBO (Natural
Bond Orbital) [13,24], we found a standard AuC@C bonding with
a good overlapping of <Au|C3> and <Au|C4> equal to 0.65 and 0.65,
respectively, and an orbital electronic occupation of AuC3 and Au
C4 equal to 1.8.
To complete this study, neutral and cationic complexes energy
differences were also carried out between minima. Then, the computed DG value 50 kcal mol1 from B ? C required for the chlorine
elimination at DFT levels and 48 kcal mol1 at MP2. The same result was seen for the cationic A ? A+ complexes showing again
lower energy closer to 50 kcal mol1. In conclusion, according to
the lower energy (DG), we suggest a direct and fast equilibrium
in situ between cationic and neutral gold complexes in phenol synthesis because the lower computed (DG) energy between cationic
and neutral complexes. In addition, theses values give more credibility in the use of the cationic complex reaction rather the neutral. Also, the correlation effect described especially in each
method in MP2, improves the convergence and accuracy of the metal-ligand bonding [18,22].

3.4. Cationic model [(benzene)PH3Au]+: ML2

It was also tempting to simulate the gold precursor [Au] in the
main reaction drawn in Fig. 1 by using another hypothetic catalyst
model ML2 i.e. [(benzene)PH3Au]+ (D) (Fig. 7). We focus here on the

biphenylPH2 AuCl  Cl ! biphenylPH2 Au

Different calculations were undertaken on (C) and only the real
minimas are considered. As a result of MP2 and DFT optimization
on (C) (see Fig. 6), we obtained short distances of AuC3 and
AuC4 respectively, closer to 2.48/2.60 in MP2 (Table 4, rst

Fig. 7. DFT/B3LYP optimized structure of cationic model of [(benzene)PH3Au]+ (D).

Orange ball = P; Gray = C and Yellow = Au. (For interpretation of the references to
colour in this gure legend, the reader is referred to the web version of this article.)

Table 5
Structural optimization of [(benzene)PH3Au]+ (D).

Fig. 6. Sketch of the third optimized model [(biphenyl)PH2Au]+ (C); Orange ball = P;
Gray = C and Yellow = Au. (For interpretation of the references to colour in this
gure legend, the reader is referred to the web version of this article.)

MP2/LANL2DZ/6-311g++(d,p)
B3LYP/LANL2DZ/6-311g++(d,p)
CCSD

AuC3

AuC4

AuC2

AuP

2.27
2.29
2.20

2.39
2.41
2.35

3.36
3.32
3.30

2.28
2.30
2.26

M. Touil et al. / Journal of Molecular Structure: THEOCHEM 957 (2010) 2125

optimization of the cationic model (D) at different level of theory:

MP2 and B3LYP/(LANL2DZ). The results of our computation are
summarized in Table 5, (here only the real minimas were considered). At rst observation, the preferred attack of benzene is frontal. Secondly, the MP2 and B3LYP distances give a standard AuC3,4
bonds equal to 2.27/2.39 and 2.29/2.41 , respectively. The structure optimization of (D) adopts a dissymmetric mode of coordination of benzene g2CC double bond. Meanwhile, with CCSD
calculation, we observe a decreases of AuC bond 2.20 and conrmed also dissymmetric g2-olengold coordination but closer to
standard CC bonding. This kind of complexation was also seen in
Crbenzene complexes [9a,21] even though the metal coordination
remains different (g6 rather weak g2 in (B)). But, we predict that
the cationic precursor (usually considered as more reactive species
in situ with 14 electron as total electronic account) should have a
good reactivity than the neutral because theoretically, he possesses
two Frontier orbitals (OF) lying at high energy [23] exiting potentially in ML2 entities which have (a0 ) and (a00 ) symmetry in respect
of the symmetry Cs or a0 and a00 in symmetry Cs. Most of them are
pointed to every incoming ligand in ML2 and can react strongly
more than in ML3 and can react easily with the substrate. The
charge positive on ML2 may also give lower the energy of these
frontier orbitals [24] and leads to strong interaction with each
incoming bonds from substrate and provide a good catalytic reaction. So by comparing the neutral ML3 and ML2 (the cationic form),
a substantial electronic changes in gold conguration should occur
and induces the reactivity of the metal in the catalytic process [9a].
4. Conclusion
DFT, MP2 and CCSD computations were performed to study the
expected C@C double bond weakly coordinated to gold (I) in the
[(biphenyl-NMe2)Ph2PAuCl] precursor used in the phenol synthesis. Different models were performed showing different linkage
of C@C bonds on the metal. Thus, the computed structure converged by a weak coordination of CC to the gold (I). At DFT levels,
the computed AuC bonds remains higher resulting of the higher
polarization of the biphenyl ligand. Meanwhile, for the cationic
pre-catalyst, despite the high dispersion effect of biphenyl ring,
the MP2 and CCSD calculations reproduced the tendency of the
bond distances and angles of the olengold coordination. Therefore, we suggest a possible equilibrium in situ between the cationic
and neutral gold related to the lowest computed energy differences
in (DG). We notice also that the cationic model has less electron
rich counterparts and offers an important reactivity in situ than
the neutral gold (I) in the phenol formation due to the changes
in the electronic structure.
Acknowledgements
Raba thanks DAAD for support of this work at Heidelberg University and Dr. Tom Cundari at University of North Texas, CASCaM

25

for his comments on the manuscript. M.A.O. acknowledges partial

support of his contributions by the Robert A. Welch Foundation
(Grant B-1542), the Texas Advanced Research Program (Grant
009741-0089-2007) and the National Science Foundation (Grants
CHE-0349313 and CHE-0911690).
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