OXIDATIVE-ADDITION REACTIONS OF S-S AND SE-SE BONDS TO MO2 AND W2 QUADRUPLE BONDS

Oxidative-addition chemistry of the quadruply bonded molybdenum and tungsten M2Cl4(dppm)2 dimers (dppm = bis(diphenylphosphino)methane) has been investigated by using diphenyl disulfide, diphenyl diselenide, dichloromethane, and chlorine as the oxidizing agents. The products to be discussed here are the following: W2(-SPh)2Cl4(dppm)2 (1), W2(-SPh)(-Cl)-Cl4(dppm)2 (2), W2(-SePh)2Cl4(dppm)2 (3), W2(-SePh)(-Cl)Cl4(dppm)2 (4), W2(-Cl)2Cl4(dppm)2 (5), Mo2(-SPh)(-Cl)Cl4(dppm)2 (6), and Mo2(-Cl)2Cl4(dppm)2 (7). The structural characterization of compounds 1, 4, and 6 is reported here. Pertinent crystal data are as follows: 1, P1, a = 12.991 (2) , b = 13.851 (3) , c = 11.693 (2) , = 111.28 (2), = 103.43 (2), = 89.03 (2), V= 1903 (1) 3, W-W = 2.787 (1) ; 4, Pna21, a = 39.335 (10) , b = 15.371 (4) , c = 11.774 (3) , V= 7119 (5) 3, W-W = 2.708 (2) ; 6, P21/n, a = 12.096 (4) , b = 24.474 (6) , c = 23.329 (5) , = 100.73 (2), V = 6786 (3) 3, Mo-Mo = 2.788 (1) . 1988, American Chemical Society. All rights reserved.

OXIDATIVE-ADDITION REACTIONS OF S-S AND SE-SE BONDS TO MO2 AND W2 QUADRUPLE BONDS Academic Article