Structural, Far-infrared & 31P Nuclear Magnetic Resonance Studies of Two Co-Ordinate Complexes of Tris(2,4,6,- trimethoxyphenyl) phosphine with Gold (I) Halides
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The complexes [AuX(tmpp)][X = Cl, Br or I; tmpp = tris(2,4,6-trimethoxyphenyl)phosphine] were prepared by reaction of tmpp with [AuX(Me2S)] or [AuX2]-. The crystalline compounds are isomorphous with the corresponding complexes of Cu and Ag, with Au-P 2.253(5), 2.255(4), 2.239(7), Au-X 2.303(6), 2.413(2), 2.586(2)Šand P-Au-X 176.0(2), 175.9(1), 177.7(2)The Au O contacts involving the nearest o-methoxy oxygen atoms on the three phenyl groups in the ligand are: 3.15(1), 3.08(1), 2.92(2)(chloride); 3.13(2), 3.11(1), 2.96(1)(bromide); 3.01(2), 3.10(1), 3.09(2)Ũiodide). The complexes [AuX(tmpp)] were characterized by far-IR spectroscopy [(Au-X) 313, 218, 183 cm-1.; X = Cl, Br, I] and by 31P NMR spectroscopy in acetonitrile [(31P)-35.9, -31.8, -23.9]. All members of the series [MX(tmpp)](M = Cu, Ag or Au; X = Cl, Br or I) are now known (although the Agl complex has so far only been detected in solution). The M-X bond properties in this series show trends which reveal the presence of relativistic effects in the M = Au case. Reaction of [AuX(tmpp)] with tmpp in a 1 : 1 mole ratio in solution results in displacement of X- to yield [Au(tmpp)2]+[(31P)-24.9]. Unlike the corresponding PPh3complexes, [AuX(tmpp)] show no evidence of 1J(197Au31P) spin-spin splitting in their solid-state 31P cross polarization magic angle spinning NMR spectra. A simple one-pot synthesis of the known gold(I) complex [NBu4][Aul2] from metallic gold was achieved.
Journal of the Chemical Society. Dalton Transactions
Copyright 1995 Royal Society of Chemistry. Please refer to the journal link for access to the definitive, published version.