SYNTHESIS, STRUCTURE, AND REACTIVITY OF HMO2(CO)9(NO)

Treatment of (Na)(HMo2(CO)10) with acidic sodium nitrite affords HMo2( CO)0(NO) (1) in 32% yield. Several derivatives of 1, HMo2(CO)8(L)(NO) (2, L = PCy3; 3, L = PPh3; 4, L = P(p-C6H4OMe)3), HMo2(CO)7(L)2(NO) (5 , L = P(OMe)3; 6, L = Ph2PH), HMo2(CO)7(MeNC)2(NOeq) (7), HM02(CO)7(iP rNC)2(NO(ax)) (8), HMo2(CO)7(PCY3)(nPrNC)(NO) (9), and (NMe4)(HM02(CO) 7(eta2-S2CNEt2XNO)) (10), have been synthesized. X-ray crystal structu ral analyses for 1, 2, 6, and 9 were carried out. 1: triclinic, P1BAR, Z = 1, a 6.810(2), b 6.906(3), c 8.741(2) angstrom, a 103.50(2), beta 68.85(2), gamma 92.04(2)-degrees, V 372.3(2) angstrom3, R = 0.020, R( W) = 0.025. 2: monoclinic, P2(1)/c, Z = 4, a 12.179(l), b 14.983(l), c 17.068(2) angstrom, beta 92.126(8)-degrees, V 3112.4(5) angstrom3, R = 0.035, R(W) = 0.041. 6: monoclinic, P2(1)/c, Z = 4, a 9.402(2), b 16 .614(3), c 21.635(3) angstrom, beta 92.58(3)-degrees, V 3376(l) angstr om3, R = 0.034, R(W) = 0.035. 9: orthorhombic, Pbca, Z = 8, a 17.113(7 ), b 17.715(2), c 22.954(3) angstrom, V 6959(3) angstrom3, R = 0.036, R(W) = 0.038.