Phosphido bridged heterodinuclear (Mn/Fe, Mn/Cr, Mn/W) complexes

Article abstract of DOI:10.1016/0022-328X(94)05028-A

Treatment of (MeCp)Mn(CO)2(Ph2PLi), generated in situ, with M(CO)n(THF) in THF at -60 deg C followed by cation exchange, provides <(MeCp)Mn(CO)2(μ-PPh2)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)(μ-PPh2) (7) which contains a metal-metal (Mn-Fe) bond.Photolysis of 6 also results in formation of a metal-metal bond, and <(MeCp)MnW(CO)6(μ-PPh2)> (8) was isolated.Complex 8 reacts with CO and MeNC to afford 6 and <(MeCp)Mn(CO)2(μ-PPh2)W(CO)4(MeNC)> (9), respectively.X-raydiffraction studies of <(MeCp)Mn(CO)2>(μ-Ph2PPPh2) (4), 6, and 9 were carried out to give data as follows. 4: P2₁/n, Z=4, a = 9.6875(9), b = 12.191(1), c = 15.382(2) Angstroem, β = 107.20(1) deg, V = 1735.4(4) Angstroem, R = 0.032, R_w = 0.036. 6: Pbca, Z=8, a = 13.197(2), b = 20.544(4), c = 24.953(4) Angstroem, V = 6765(2) Angstroem, R = 0.031, R_w = 0.031. 9: P2₁/c, Z=4, a = 14.252(1), b = 12.816(3), c = 19.176(2) Angstroem, β = 96.255(9) deg, V = 3481.6(9) Angstroem, R = 0.035, R_w = 0.038.Keywords: Iron; Manganese; Chromium; Phosphide; Heterobimetallics; Metal carbonyl anions