HETEROBIMETALLIC COMPLEXES WITH PHENYLCYCLOPENTADIENYL LIGAND - SYNTHESES AND STRUCTURES OF TRICARBONYLCHROMIUM - ETA(6),ETA(5)-PHENYLCYCLOPENTADIENYL - TRANSITION-METAL COMPLEXES

A new synthetic method of heterobimetallic complexes bridging with a p i,pi-phenylcyclopentadienyl ligand, um-eta(6),eta(5)-phenylcyclopentad ienyl-transition metal complexes, was developed through the reactions of (eta(6)-C6H5C5H5)Cr(CO)(3) or its sodium salt with transition metal complexes. The method is suitable far most transition metal elements with the advantages of easy manipulation, mild reaction conditions, an d moderate to high yields. As indicated by H-1 NMR spectra, the intera ctions between the two eta systems of phenyl and cyclopentadienyl ring s were weak. X-ray crystal structures of seven complexes were studied. Compound 23, [eta(6)-C6H5Cr(CO)(3)](2)C10H10, crystallizes in orthorh ombic space group Pbca with cell constants a = 29.616(8) Angstrom, b = 12.861(5) Angstrom, c = 12.397(7) Angstrom, V = 4721(6) Angstrom(3), Z = 8, R = 0.045, and R(w) = 0.035. Compound 3, (eta(6)-C6H5C9H7)Cr(CO )(3), crystallizes in monoclinic space group P2(1)/c with cell constan ts a = 7.901(3) Angstrom, b = 14.799(2) Angstrom, c = 12.917(2) Angstr om, beta = 99.72(2)degrees, V = 1488.7(4) Angstrom(3), Z = 4, R = 0.04 4, and R(w) = 0.051. Compound 7, )(3)(eta(6),eta(5)-C6H5C5H4)Ti(CO)(2) (eta(5)-C5H5) crystallizes in monoclinic space group P2(1)/c with cell constants a = 12.361(4) Angstrom, b = 12.387(6) Angstrom, c = 12.531( 7) Angstrom, beta = 93.38(4)degrees, V = 1930 Angstrom(3), Z = 4, R = 0.047, and R(w) 0.048. Compound 13, Cr(CO)(3)(eta(6),eta(5)-C6H5C5H5)M o(CO)(3)Br, crystallizes in monoclinic space group P2(1)/c with cell c onstants a = 14.685(2) Angstrom, b = 8.509(3) Angstrom, c = 14.960(3) Angstrom, beta = 104.46(1)degrees, V = 1810.0(7) Angstrom(3), Z = 4, R = 0.037, and R(w) = 0.037. Compound 19, Cr(CO)(3)(eta(6),eta(5)-C6H5C 9H6)Mo(CO)(3), crystallizes in triclinic space group P-1 with cell con stants a = 11.660(4) Angstrom, b = 12.578(5) Angstrom, c = 6.987(2) An gstrom, alpha = 100.03(3)degrees, beta = 104.19(2)degrees, gamma = 71. 99(3)degrees, V = 939.3(6) Angstrom(3), Z = 2, R = 0.048, and R(w) = 0 .065. Compound 21, Cr(CO)(3)(eta(6),eta(5)-C6H5C5H4)Ru(PPh(3))(2)Cl, c rystallizes with one molecule of EtOH in triclinic space group P-1 wit h cell constants a = 14.033(4) Angstrom, b = 16.163(6) Angstrom, c = 1 0.411(3) Angstrom, alpha = 104.22(3)degrees, beta = 103.50(2)degrees, gamma = 90.81(3)degrees, V = 2219(1) Angstrom(3), Z = 2, R = 0.081, an d R(w) = 0.096. Compound 22, Cr(CO)(3)(eta(6),eta(5)-C6H5C5H4)Co(CO)(2 ), crystallizes in orthorhombic space group P2(1)2(1)2(1) with cell co nstants a = 15.083(5) Angstrom, b = 16.391(5) Angstrom, c = 6.351(4) A ngstrom, V = 1570(1) Angstrom(3), Z = 4, R = 0.036, and R(w) = 0.039. The trans configurations of the two metal atoms in these molecules wer e found as expected; the phenyl and cyclopentadienyl or indenyl rings in the molecules were found to be not coplanar.