STRUCTURAL CHARACTERIZATION OF BIDENTATE CARBOXYLATE DERIVATIVES OF COPPER(I) BISTRIPHENYLPHOSPHINE
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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 CuO bond distances differing by 0.234(6) . 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 (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) , = 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) , a = 115.46(14), = 97.54(16), = 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) , = 118.85(1), = 105.85(1), = 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) , = 63.71(1), = 79.08(1), = 75.20(1), Z = 2, R = 7.6%. 1994.
