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• W2048600629 abstract "The complexes (Ph3P)2Cu(carboxylate) (carboxylate = acetate (1), hippurate (2), vinyl acetate (3), fluorenate (4)) have been prepared and their solid-state structures determined crystallographically. The copper(I) center in all four structures exhibits a distorted tetrahedral geometry, with varying degrees of asymmetric bidentate binding of the carboxylate ligand. For example, in complex 2 the hippurate ligand displays the greatest extent of asymmetry with the two CuO bond distances differing by 0.234(6) Å. The structures of all four derivatives were each shown to be the same both in the solid-state and in dichloromethane solution based on infrared spectroscopy. The magnitude of Δ (va(CO2−)-vs(CO2−)) in these copper(I) derivatives, determined to be quite similar to the corresponding ionic values, is used as constituting a diagnosis for asymmetric bidentate binding of the carboxylate ligand. Although all four complexes are structurally quite similar, only the fluorenate derivative which affords a resonance-stabilized carbanion upon carbon dioxide extrusion undergoes the decarboxylation reaction. Crystal data for 1: space group P21/c, a = 18.085(5), b = 10.977(2), c = 17.979(5) Å, β = 115.62(2)°, Z= 4, R =3.91%. Crystal data for 2: space group P1, a = 9.96(2), b = 14.68(3), c = 14.96(3) Å , a = 115.46(14), β = 97.54(16), η = 102.31(15)°, Z = 2, R=5.84%. Crystal data for 3: space group P1, a = 12.755(3), b = 13.125(2), c = 12.572(2) Å, α = 118.85(1), β = 105.85(1), η = 97.65(1)°, Z = 2, R =4.08%. Crystal data for 4: space group P1, a = 11.554(1), b = 15.217(2), c = 15.285(2) Å, α = 63.71(1), β = 79.08(1), η = 75.20(1)°, Z = 2, R = 7.6%." @default.
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• W2048600629 date "1994-12-01" @default.
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• W2048600629 title "Structural characterization of bidentate carboxylate derivatives of copper(I) bistriphenylphosphine" @default.
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