PHOSPHIDO-BRIDGED HETERODINUCLEAR (MN/FE, MN/CR, MN/W) COMPLEXES

Treatment of (MeCp)Mn(CO)(2)(Ph(2)PLi), generated in situ, with M(CO)(n)(THF) in THF at -60 degrees C followed by cation exchange, provides [Et(4)N][(MeCp)Mn(CO)(2)(mu-PPh(2))M(CO)n] (3, M = Fe, n = 4; 5, M = Cr, n = 5; 6, M = W, n = 5). Complex 3 reacts with NO+BF4- to give (MeCp)MnFe(CO)(4)(NO)(mu-PPh(2)) (7) which contains a metal-metal (Mn-Fe) bond. Photolysis of 6 also results in formation of a metal-metal bond, and [Et(4)N][(MeCp)MnW(CO)(6)(mu-PPh(2))] (8) was isolated. Complex 8 reacts with CO and MeNC to afford 6 and [Et(4)N][(MeCp)Mn(CO)(2)(mu-PPh(2))W(CO)(4)(MeNC)] (9), respectively. X-ray diffraction studies of [(MeCp)Mn(CO)(2)](mu-Ph(2)PPPh(2)) (4), 6, and 9 were carried out to give data as follows. 4: P2(1)/n, Z = 4, a = 9.6875(9), b = 12.191(1), c = 15.382(2) Angstrom, beta = 107.20(1)(degrees), V = 1735.4(4) Angstrom, R = 0.032, R(w) = 0.036. 6: Pbca, Z = 8, a = 13.197(2), b = 20.544(4), c = 24.953(4) Angstrom, V = 6765(2) Angstrom, R = 0.031, R(w) = 0.031. 9: P2(1)/c, Z = 4, a = 14.252(1), b = 12.816(3), c = 19.176(2) Angstrom, beta = 96.255(9)(degrees), V = 3481.6(9) Angstrom, R = 0.035, R(w) = 0.038.