Inorganic Chemistry
COMMUNICATION
Table 2. Atomic Partial Charges and Polarization of the CꢀO σ and π Bonds in [(Mes3P)Au(CO)]þ, [Au(CO)]þ, and Free CO
Taken from NBO Calculations
compound
q(C)
q(O)
σCꢀO
π(1)CꢀO
π(2)CꢀO
[(Mes3P)Au(CO)]þ
[Au(CO)]þ
CO
0.56
0.48
0.50
ꢀ0.33
ꢀ0.27
ꢀ0.50
C, 31.0%; O, 69.0%
C, 31.2%; O, 68.8%
C, 29.0%; O, 71.0%
C, 26.4%; O, 73.6%
C, 28.1%; O, 71.9%
C, 22.8%; O, 77.2%
C, 26.4%; O, 73.6%
C, 28.1%; O, 71.9%
C, 22.8%; O, 77.2%
bond order (NBO)37 method. Table 2 shows that the contribu-
tion of the carbon atomic orbitals to the σ and π orbitals in the
latter complexes is clearly larger than that in free CO. The
calculated partial charges indicate that the oxygen atom in
[(Mes3P)Au(CO)]þ and in [Au(CO)]þ is much less negatively
charged, while the carbonyl carbon atom becomes a bit more
positive in the former complex but slightly less positive in the
latter species. The calculated overall charge donations are 0.23e
for (Mes3P)Auþ r CO and 0.21e for Auþ r CO. Analysis of
the electronic structure of [(Mes3P)Au(CO)]þ and [Au(CO)]þ
suggests that the blue shift of the CO stretching mode is primarily
due to the electrostatic effect of the metal fragment on the
polarization of the CꢀO bond.
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In summary, we describe the synthesis of an easily isolable
gold carbonyl complex using readily available starting materials.
We are currently exploring the catalytic properties of [(Mes3P)-
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auxiliary ligands to stabilize gold carbonyl species.
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’ ASSOCIATED CONTENT
S
Supporting Information. X-ray crystallographic data in
b
CIF format, further details of the synthesis and characterization,
computational methods, additional data, and figures. This material
’ AUTHOR INFORMATION
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Corresponding Author
*E-mail: dias@uta.edu (H.V.R.D.), frenking@chemie.uni-marburg.
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’ ACKNOWLEDGMENT
(31) For comparison, the 13CN signals in the 13C{1H} NMR spectra
of Ph3PAuCN and Et3PAuCN show two bond PꢀC couplings (2JC,P) of
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This work was supported by the National Science Foundation
(Grant CHE-0845321 to H.V.R.D. and Grant CHE-0840509)and
the Robert A. Welch Foundation (Grant Y-1289 to H.V.R.D.).
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