SYNTHESIS, CHARACTERIZATIONS, AND STRUCTURES OF GROUP-IV METAL CHROMIUM COMPLEXES BRIDGED BY THE BENZYLOXIDE GROUP

Bimetallic complexes, (eta-5-C5H5)2MX[(mu-OCH2C6H5)Cr(CO)3] (M = Ti, X = Cl (1) or Br (2); M = Zr, X = CH2C6H5 (3)), were prepared by reacting (HOCH2C6H5)Cr(CO)3 with the appropriate titanocene or zircocene alkyl. The complex, (eta-5-C5H5)2Zr[(mu-OCH2C6H5)Cr(CO)3]2 (4), was synthesized by reacting 2 molar equivalents of (HOCH2C6H5)Cr(CO)3 with (eta-5-C5H5)2Zr(CH3)2. These complexes have been characterized by elemental analysis, IR, H-1, and C-13 NMR spectroscopy. The complex 2 crystallizes in the monoclinic space group P2(1)/a with a = 7.892(l), b = 21.167(2), c = 11.345(3) angstrom, beta = 92.00(2)-degrees, V = 1915.4(6) angstrom 3 and Z = 4. However, the complex 4 crystallizes in the triclinic space group P1BAR with a = 7.984(2), b = 11.349(4), c = 16.074(4) angstrom, alpha = 96.14(3)-degrees, beta = 101.06(2)-degrees, gamma = 93.45(2)-degrees, V = 1416.7(4) angstrom 3, and Z = 2. From the X-ray structures, IR, and NMR spectroscopy, the (C6H5)Cr(CO)3 moiety seems unperturbed by the early metal center.