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Heterobimetallic Complexes with Phenylcyclopentadienyl Ligand:  Syntheses and Structures of Tricarbonylchromium−η65-Phenylcyclopentadienyl−Transition Metal Complexes1

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posted on 1997-03-26, 00:00 authored by Changtao Qian, Jianhua Guo, Jie Sun, Jian Chen, Peiju Zheng
A new synthetic method of heterobimetallic complexes bridging with a π,π-phenylcyclopentadienyl ligand, tricarbonylchromium−η65-phenylcyclopentadienyl−transition metal complexes, was developed through the reactions of (η6-C6H5C5H5)Cr(CO)3 or its sodium salt with transition metal complexes. The method is suitable for most transition metal elements with the advantages of easy manipulation, mild reaction conditions, and moderate to high yields. As indicated by 1H NMR spectra, the interactions between the two π systems of phenyl and cyclopentadienyl rings were weak. X-ray crystal structures of seven complexes were studied. Compound 23, [η6-C6H5Cr(CO)3]2C10H10, crystallizes in orthorhombic space group Pbca with cell constants a = 29.616(8) Å, b = 12.861(5) Å, c = 12.397(7) Å, V = 4721(6) Å3, Z = 8, R = 0.045, and Rw = 0.045. Compound 3, (η6-C6H5C9H7)Cr(CO)3, crystallizes in monoclinic space group P21/c with cell constants a = 7.901(3) Å, b = 14.799(2) Å, c = 12.917(2) Å, β = 99.72(2)°, V = 1488.7(4) Å3, Z = 4, R = 0.044, and Rw = 0.051. Compound 7, Cr(CO)365-C6H5C5H4)Ti(CO)25-C5H5), crystallizes in monoclinic space group P21/c with cell constants a = 12.361(4) Å, b = 12.487(6) Å, c = 12.531(7) Å, β = 93.48(4)°, V = 1930 Å3, Z = 4, R = 0.047, and Rw = 0.048. Compound 13, Cr(CO)365-C6H5C5H4)Mo(CO)3Br, crystallizes in monoclinic space group P21/c with cell constants a = 14.685(2) Å, b = 8.509(3) Å, c = 14.960(3) Å, β = 104.46(1)°, V = 1810.0(7) Å3, Z = 4, R = 0.037, and Rw = 0.037. Compound 19, Cr(CO)365-C6H5C9H6)Mn(CO)3, crystallizes in triclinic space group P-1 with cell constants a = 11.660(4) Å, b = 12.578(5) Å, c = 6.987(2) Å, α = 100.03(3)°, β = 104.19(2)°, γ = 71.99(3)°, V = 939.3(6) Å3, Z = 2, R = 0.048, and Rw = 0.065. Compound 21, Cr(CO)365-C6H5C5H4)Ru(PPh3)2Cl, crystallizes with one molecule of EtOH in triclinic space group P-1 with cell constants a = 14.033(4) Å, b = 16.163(6) Å, c = 10.411(3) Å, α = 104.22(3)°, β = 103.50(2)°, γ = 90.81(3)°, V = 2219(1) Å3, Z = 2, R = 0.081, and Rw = 0.096. Compound 22, Cr(CO)365-C6H5C5H4)Co(CO)2, crystallizes in orthorhombic space group P212121 with cell constants a = 15.083(5) Å, b = 16.391(5) Å, c = 6.351(4) Å, V = 1570(1) Å3, Z = 4, R = 0.036, and Rw = 0.039. The trans configurations of the two metal atoms in these molecules were found as expected; the phenyl and cyclopentadienyl or indenyl rings in the molecules were found to be not coplanar.

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