Synthesis of a coordinatively labile gold(III) methyl complex

Article abstract of DOI:10.1021/om200327a

Stable and isolable cyclometalated monomethyl Au(III) complexes are readily available from the precursor (tpy)Au(Me)Cl, prepared from (tpy)AuCl₂ and excess SnMe₄. Reaction of (tpy)Au(Me)Cl with suitable silver salts generates (tpy)Au(Me)(X) (X = OAc, OTf). Ligand exchange reactions with (tpy)Au(Me)(OTf) provide the cationic monomethyl Au(III) adducts [(tpy)Au(Me)(L)][OTf] (L = PPh₃, THT).

Full text of DOI:10.1021/om200327a

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pubs.acs.org/Organometallics
Synthesis of a Coordinatively Labile Gold(III) Methyl Complex
Ajay Venugopal,† Anthony P. Shaw,‡ Karl W. T€ornroos,§ Richard H. Heyn,*,† and Mats Tilset*,‡
†SINTEF Materials and Chemistry, P.O. Box 124, Blindern, 0314 Oslo, Norway
‡Centre of Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern,
0315 Oslo, Norway
§Department of Chemistry, University of Bergen, Allꢀegaten 41, 5007 Bergen, Norway
S Supporting Information
b
ABSTRACT: Stable and isolable cyclometalated monomethyl
Au(III) complexes are readily available from the precursor
(tpy)Au(Me)Cl, prepared from (tpy)AuCl2 and excess SnMe4.
Reaction of (tpy)Au(Me)Cl with suitable silver salts generates
(tpy)Au(Me)(X) (X = OAc, OTf). Ligand exchange reactions
with (tpy)Au(Me)(OTf) provide the cationic monomethyl
Au(III) adducts [(tpy)Au(Me)(L)][OTf] (L = PPh3, THT).
he chemistry of gold has been growing by leaps and bounds
the past several years, in large part driven by the utilization of
The monomethyl Au(III) compound (tpy)Au(Me)Cl (1) was
T
obtained in low yield (8%) from the reaction between
7
carbophilic π-acidic gold compounds as catalysts for organic
transformations. While simple Au(I) or Au(III) salts are active,
the ready, in situ generation of a large variety of coordinatively
labile LAu(I)þ species (L = phosphine, N-heterocyclic carbene,
pyridine)1 has allowed the design of more sophisticated Au(I)
catalysts. On the other hand, there are only a handful of Au(III)
catalysts that have formulations more complicated than that of
AuCl3 or NaAuCl4, of which (2-pyridinecarboxylate)AuCl2 is the
most common.2 It is also problematic that the mechanisms of the
vast majority of homogeneous gold-catalyzed reactions are still
speculative;3 for example only two Au(III) catalytic intermedi-
ates have been spectroscopically identified.2g,m In addition to
redox-neutral gold catalysis, there has been a recent burst of
catalytic reactions where a Au(I)ꢀAu(III) mechanistic pathway is
the current hypothesis,4 and Au(III) complexes resembling con-
jectural intermediates have been synthesized.5 The confluence of
these factors suggests that the chemistry of well-defined, coordina-
tively labile Au(III) compounds would be quite valuable for further
advancements in gold catalysis. Such species are, however, exceed-
ingly rare, and as far as we know only one coordinatively labile
Au(III) complex has been extensively studied, namely, AuMe2-
(OTf)(H2O), which was synthesized and characterized by Kochi as
early as 1977.6 We report herein the synthesis of a new cyclome-
talated Au(III) methyl species, (tpy)AuMe(Cl) (tpy = 2-p-
tolylpyridine). This is readily converted to the covalently bonded
triflate species (tpy)AuMe(OTf) (OTf = OSO2CF3), which fea-
tures a coordinatively labile OTfꢀ ligand, as evidenced by its
exchange reactions with other donor ligands.
(tpy)AuCl2 and 6-fold excess of SnMe4 in acetonitrile under
reflux conditions (see Scheme 1). SnMe4 is known to be one of
the better methylating agents for Au(III),8 although yields are
generally poor.9 The primary byproduct in the synthesis of 1 was
metallic gold (62%). An analogous reaction between (bipy)Au-
Cl2 and excess SnMe4 also proceeded in low yield and with a
large amount of metallic gold as a byproduct, although in this case
the dimethyl complex (bipy)AuMe2 was obtained.10 The synth-
esis of 1 is also in marked contrast to the high-yield synthesis of
related monoaryl Au(III) compounds, such as (damp)Au(Ph)Cl
from (damp)AuCl2 and HgPh2 (damp = C6H4CH2NMe2).11
Compound 1 was characterized by NMR spectroscopy, elemental
analysis, and mass spectrometry.12 It is soluble in dichloromethane
and toluene, and the isolated compound is air-stable at room tem-
perature for at least several days. A CD2Cl2 solution of 1 exhibited a
single resonance for the methyl group bound to Au at δ 1.53 and 9.2
in the 1H and 13C NMR spectra, respectively. Cross-peaks in a 1H
NOE experiment between the Au-Me protons and 60-H, and
between 60-H and the tolyl methyl protons on the tpy ligand,
provided evidence for the coordination of the Au-methyl group trans
to the pyridyl N-atom. Compound 1 did not react with the neutral
ligands triphenylphosphine, acetonitrile, acetone, diethyl ether,
and water.
Treatment of 1, however, with 1 equiv of silver acetate in either
acetonitrile or dichloromethane for 8 h at room temperature
Received: April 18, 2011
Published: May 25, 2011
r
2011 American Chemical Society
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Scheme 1. Synthesis and Reactivity of 1 and 3
Figure 2. ORTEP view of the solid-state structure of 3 with 50%
probability ellipsoids. Hydrogen atoms are removed for clarity. Pertinent
bond distances (Å) and angles (deg): Au1ꢀC1, 1.995(2); Au1ꢀC13,
2.030(2); Au1ꢀO1, 2.1382(17); Au1ꢀN1, 2.1092(19); S1ꢀO1,
1.4809(18); S1ꢀO2, 1.4295(19); S1ꢀO3, 1.4304(18); C1ꢀAu1ꢀ
C13, 94.34(10); C1ꢀAu1ꢀO1, 171.53(8); C1ꢀAu1ꢀN1, 82.20(8);
C13ꢀAu1ꢀO1, 91.82(8); C13ꢀAu1ꢀN1, 176.47(8); O1ꢀAu1ꢀN1,
91.69(7); Au1ꢀO1ꢀS1, 129.06(11).
group is trans to an N-heterocyclic carbene.16 The Au1ꢀO1 distance
is intermediate between the corresponding distance for the neutral
(ppy)Au(OAc)2 (ppy = 2-phenylpyridine), 2.018(6) Å,17 and the
cationic[(pmpy)Au(OAc)(py)][ClO4] (pmpy = 2-phenyl-3-methyl-
pyridine), 2.13(3) Å.18 The five atoms making up the central
coordination geometry (Au1, C1, C13, O1, and N1) are nearly
planar; the maximum deviation from the mean plane calculated from
these atoms is only 0.067 Å. In the extended structure, molecules of 2
stack through partially overlapping tpy ligands, and the closest
distance between the aromatic rings of adjacent molecules is 3.3 Å.
The zigzag stacking pattern is governed by a crystallographic
inversion symmetry element that eliminates close AuꢀAu contacts.
Similar to the synthesis of 2, reaction of 1 with 1 equiv of silver
triflate (AgOTf) in 2,2,2-trifluoroethanol provided (tpy)Au(Me)
(OTf) (3). The use of 2,2,2-trifluoroethanol as solvent is key for
the successful synthesis and isolation of 3. In other solvents, such
as dichloromethane or acetonitrile, this reaction did not proceed
to completion, and 3 could not be isolated as a pure compound.
In solution, the composition and coordination stereochemistry
of 3 were unequivocally established by NMR experiments
analogous to those utilized for 1 and 2.12 The solid-state struc-
ture19 was again shown to be the same as the solution structure;
see Figure 2. Only two other structures with covalent, unidentate
AuꢀOTf bonding could be found in the literature: cis-Me2Au-
(H2O)(OTf)20 and (o-Tol)3PAu(OTf).21 The Au-OTf structural
parameters of 3 are intermediate between these two; the
Au1ꢀO1 and SꢀO bond distances more closely resemble the
corresponding parameters of the latter, Au(I) triflate compound,
while the Au1ꢀO1ꢀS1 bond angle is closer to that in the former
example. The Au1ꢀO1 bond distance closely matches the cor-
responding AuꢀO distance in the Au(III) nitrate (ppy)Au-
(CH2COCH3)(ONO2).14b Apart from the longer AuꢀO bond,
the coordination geometry of 3, i.e., the bond distances, bond
angles, and planarity of the central core, are very similar to the
corresponding values in 2. This similarity extends to the crystal-
line stacking motif exhibited by 3, although the shortest distance
between stacked aromatic rings is now 3.4 Å.
Figure 1. ORTEP view of the solid-state structure of 2 CH2Cl2 with
3
50% probability ellipsoids. CH2Cl2 solvent of crystallization and hydro-
gen atoms are removed for clarity. Pertinent bond distances (Å) and
angles (deg): Au1ꢀC1, 2.0005(19); Au1ꢀC13, 2.027(2); Au1ꢀO1,
2.0861(15); Au1ꢀN1, 2.1165(19); C1ꢀAu1ꢀC13, 94.21(9);
C1ꢀAu1ꢀO1, 173.45(7); C1ꢀAu1ꢀN1, 81.36(7); C13ꢀAu1ꢀO1,
91.04(8); C13ꢀAu1ꢀN1, 174.69(7); O1ꢀAu1ꢀN1, 93.59(7).
resulted in nearly quantitative formation of (tpy)Au(Me)(OAc)
(2). The identity of this compound was established by NMR spec-
1
troscopy, elemental analysis, and mass spectrometry. A H NOE
experiment showed the same two sets of cross-peaks as observed for
1, between the Au-Me protons, 60-H, and the tolyl methyl protons,
which confirmed that 2 has a solution phase coordination stereo-
chemistry analogous to 1.12 In this instance, the solid-state stereo-
chemistry was determined by single-crystal X-ray diffraction.13 As
shown in Figure 1, 2 has the expected (slightly distorted) square-
planar coordination geometry with the Au-Me group indeed located
trans to the pyridyl N-atom. The bond distances and angles are not
unusual and correspond to reported values for cyclometalated Au
complexes14 and Au(III)-Me complexes.15 The Au1ꢀC13 distance of
2.027(2) Å is significantly shorter than the corresponding distances in
the monomethyl Au(III) complexes (Idipp)AuI2Me (2.185(11) Å)
and (Idipp)AuMeI(NC4H4O2) (2.086(3) Å), where the methyl
As with 1, no reactions were observed between 2 and the
neutral ligands triphenylphosphine, acetonitrile, acetone, and
diethyl ether in CD2Cl2. In contrast, similar experiments with 3
containing the more labile OTfꢀ ligand resulted in ligand ex-
change reactions and the formation of cationic, monomethyl
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of Au(III). In particular, 3 and its congeners may well prove to be
important mechanistic probes of catalytic reactions involving
Au(III) intermediates, which will hopefully lead to new insights
into these transformations. For instance, while reactions cata-
lyzed by gold are generally proposed to involve π-bound alkynes,
alkenes, or arenes as intermediates, no well-characterized Au(III)
π-complexes of these ligands are known.24 Furthermore, the
availability of a coordination site cis to a methyl group may allow
validation of the potential of Au complexes as CꢀH activation
and functionalization catalysts for light alkanes. Improvements in
the yield of 1 and the scope of the ligand exchange reactions for 3
are the subjects of current studies within the Oslo Gold Team,
and the results of these studies will be presented in due course.
’ ASSOCIATED CONTENT
Figure 3. ORTEP view of the solid-state structure of 4 with 50% probability
ellipsoids. The triflate anion and hydrogen atoms are removed for clarity.
Pertinent bond distances (Å) and angles (deg): Au1ꢀC1, 2.0513(19);
Au1ꢀC13, 2.053(2); Au1ꢀP1, 2.4026(5); Au1ꢀN1, 2.1457(17); C1ꢀ
Au1ꢀC13, 90.06(8); C1ꢀAu1ꢀP1, 169.36(5); C1ꢀAu1ꢀN1, 80.68(7);
C13ꢀAu1ꢀP1, 91.57(6); C13ꢀAu1ꢀN1, 166.90(8); P1ꢀAu1ꢀN1,
99.25(5).
S
Supporting Information. Experimental details and full
b
characterization data (EA, MS, and 1H, 13C, 19F, 31P, COSY, and
NOESY NMR spectra) for 1ꢀ5 and crystallographic experi-
mental details and structural data for 2 CH2Cl2, 3, and 4. This
3
information is available free of charge via the Internet at http://
pubs.acs.org.
’ AUTHOR INFORMATION
Au(III) complexes (see Scheme 1). Reaction of 3 with PPh3
resulted in displacement of OTfꢀ and formation of the cationic
complex [(tpy)Au(Me)(PPh3)][OTf], 4. Coupling between P
and the Au-Me protons (δ 1.47, 3JPH = 7.7 Hz) was observed in
the 1H NMR spectrum of 4, confirming the coordination of the
PPh3 ligand to Au in solution. All other analytical and spectros-
copic data for 4 are consistent with the proposed formulation,12
which was also confirmed by determination of the solid-state
structure22 of 4, as shown in Figure 3. In contrast to 2 and 3, the
coordination sphere of 4 is severely distorted from a square-
planar geometry. While the constituent atoms of the calculated
mean square plane formed by Au1, N1, C1, and C13 show a
distance from this plane comparable to that in 2, the P1 atom is
located nearly 0.7 Å away. This distortion is likely due to packing
forces, as there is a significant number of nonbonding contacts
between the phenyl groups of any one PPh3 ligand and both
triflate anions and neighboring phenyl groups. Apart from this
distortion, there are no other anomalies in the structure; all bond
distances and angles, including the AuꢀP bond distance for P
trans to a sp2 C-atom,23 are within established ranges. The cyclo-
metalate moiety in 4 is slightly more distant from the Au center
than in 2 and 3, perhaps because of the steric requirements of the
PPh3 ligand. The supramolecular stacking of 4 is analogous to
that of 2 and 3, and the closest distance between the tpy planes of
neighboring molecules is 3.4 Å.
Corresponding Author
*(R.H.H.) Tel: þ 47 9824 3927. Fax: þ 47 2206 7350. E-mail:
richard.h.heyn@sintef.no. (M.T.) Tel: þ47 2285 5502. Fax: þ
47 2285 5441. E-mail: mats.tilset@kjemi.uio.no.
’ ACKNOWLEDGMENT
We thank the GASSMAKS program of the Norwegian Re-
search Council (grant no. 185513/I30) for generous financial
support, Drs. Ole Swang and Manik Kumer Ghosh (SINTEF)
for helpful discussions, Osamu Sekiguchi (U. Oslo) for assistance
with the MS experiments, and Aud Mjærum Bouzga (SINTEF)
and Dirk Petersen (U. Oslo) for assistance with the NMR
spectroscopy experiments.
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1
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In conclusion, we have successfully synthesized stable and
isolable examples of neutral and cationic monomethyl complexes
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3
524.18, triclinic, a = 7.2103(2) Å, b = 10.7553(3) Å, c = 12.4878(5)
Å, R = 108.622(1)°, β = 102.576(1)°, γ = 101.895(1)°, V = 855.00(5)
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0.0167, wR2 = 0.0437, CCDC number 790402.
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triclinic, a = 9.0011(3) Å, b = 9.7120(3) Å, c = 16.8412(5) Å, R =
81.2501(4)°, β = 86.7247(4)°, γ = 83.6293(3)°, V = 1444.90(8) Å3, dcalc
=
1.819 g cmꢀ3, T = 123(2) K, space group P1, Z = 2, R1 = 0.0170, wR2 =
0.0430, CCDC number 790404.
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