Syntheses and structures of new molybdenum complexes with dithiobenzoate and dimercaptotoluene ligands. Structural comparisons in a series of dithiolate-bridged dimers of molybdenum(III)

The reaction of (C/sub 5/H/sub 5/Mo(CO)/sub 3/)/sub 2/ with Zn(S/sub 3/CC/sub 6/H/sub 5/)/sub 2/ has resulted in the formation of two new molybdenum complexes containing the dithiobenzoate ligand, C/sub 5/H/sub 5/Mo(CO)/sub 2/S/sub 2/CC/sub 6/H/sub 5/ (I) and (C/sub 5/H/sub 5/Mo(S)S/sub 2/CC/sub 6/H/sub 5/)/sub 2/(II). Dimer II has been characterized by an X-ray diffraction study. The complex crystallizes in space group P2/sub 1//n with a = 16.708 (4) Angstrom, b = 22.510 (4) Angstrom, c = 6.465 (1) Angstrom, and ..beta.. = 94.88 (1)/sup 0/. The molecule consists of disulfido-bridged dimers with eta/sup 5/-C/sub 5/H/sub 5//sup -/ and bidentate S/sub 2/CC/sub 6/H/sub 5//sup -/ ligands coordinated to each molybdenum ion. A syn orientation of ligands is observed with the two dithiobenzoate ligands in approximately parallel orientations. The metal-metal distance is 3.073 (1) Angstrom, and in the Mo/sub 2/S/sub 2/ core the dihedral angle between the Mo(1)S/sub 2/ and Mo(2)S/sub 2/ planes is 126/sup 0/. The reaction of (C/sub 5/H/sub 5/Mo(CO)/sub 3/)/sub 2/ with dimercaptotoluene also results in the formation of two new products (C/sub 5/H/sub 5/Mo(CO)S/sub 2/C/sub 6/H/sub 3/(CH/sub 3/))/sub 2/ (III) is proposed to be a single isomer of low symmetry on the basis of spectral data. Irradiation of IIImore » produces (C/sub 5/H/sub 5/MoS/sub 2/C/sub 6/H/sub 3/(CH/sub 3/))/sub 2/(IV), which is isostructural with the previously reported dimer (C/sub 5/H/sub 5/Mo(SC/sub 2/H/sub 2/S))/sub 2/(V). X-ray diffraction data for IV and V are presented. IV crystallizes in space group P2/sub 1//c with a = 12.065 (2) Angstrom, b = 6.403 (2) Angstrom, C = 16.134 (3) Angstrom, and ..beta.. = 111.53 (1)/sup 0/. The cell parameters for V in space group Cmca are a = 10.440 (1) Angstrom, b = 13.199 (2) Angstrom, and c = 11.015 (2) Angstrom. The structural features of an extensive series of molybdenum(III) dimers of the general formula (C/sub 5/H/sub 5/Mo(..mu..-SR)/sub 2/)/sub 2/ are compared. 4 figures, 9 tables« less