Electrochemical Synthesis and Structural Characterization of Bis(triphenylphosphine)copper(I) FLuoroacetates

Article abstract of DOI:10.1039/DT9940000773

Bis(triphenylphosphine)copper(I) fluoroacetate complexes have been prepared by the electrochemical oxidation of copper metal in acetonitrile solutions of triphenylphosphine and mono-, di- and tri-fluoroacetic acid respectively.Recrystallization from toluene yields unsolvated mononuclear complexes 3-nF_n)>, n = 1-3, which have been characterized by single-crystal X-ray crystallographic determinations.Crystals of the three complexes are isomorphous with the acetate complex (n = 0), crystallizing in the monoclinic space group P2₁/a with cell dimensions a ca. 18.0, b ca. 11.0 and c ca. 19.3 Angstroem and β ca. 120 deg.Residuals for the complexes with n = 1, 2 and 3 were R = 0.077, 0.045 and 0.048 for 3677, 2789 and 3527 'observed' 3?(I)> reflections respectively.The bond distances Cu-P are 2.232(3), 2.222(3); 2.234(2), 2.219(2); and 2.235(2) 2.228(2) Angstroem with the corresponding P-Cu-P angles increasing from 135.0(1) to 135.8(1) to 136.7(1) deg, this latter value being the largest recorded for (+).The asymmetry of the co-ordination of the carboxylate group increases along the series with Cu-O distances of 2.144(6) and 2.363(7); 2.118(4), 2.465(6); and 2.113(4), 2.545(5) Angstroem for n = 1, 2 and 3 respectively.Crystallization of the difluoro- and trifluoro-acetate complexes from ethanol results in isomorphous orthorhombic Pb2₁a crystals (a ca. 22.2, b ca. 18.5, c ca. 9.0 Angstroem) with monodentate carboxylate and co-ordinated ethanol; the monofluoroacetate is unsolvated.For R was 0.052 for 2090 'observed' reflections with Cu P 2.248(3), 2.236(3) Angstroem and P-Cu-P 120.5(1) deg; Cu-O(carboxylate) is 2.074(8) Angstroem and Cu-O(ethanol) is 2.169(8) Angstroem.For R was 0.043 for 2350 'observed' reflections, Cu-P being 2.248(2), 2.240(2) Angstroem and P-Cu-P 120.8(1) deg; Cu-O(carboxylate) is 2.104(6) Angstroem and Cu-O(ethanol) is 2.160(6) Angstroem.

Full text of DOI:10.1039/DT9940000773

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