Manganiophosphonium salts: Synthesis, properties and structure of complexes of the type [CpMn(CO)(NO)PPh2H]BF4 and [Cp ' Mn(CO)(NO)PPh2R]X (R = H, CH3, {CpMn(CO)(NO)}; X = BF4, PF6) [German]

摘要

The reaction of [CpMn(CO)(2)NO]X (Cp = C5H5, C5H4Me = Cp'; X = BF4, PF6) with PPh2H leads to the formation of the diphenylmanganiophosphonium salts [{CpMn(CO)NO}PPh2H]X, which can be deprotonated by DABCO to give the not isolable manganiophosphane {CpMn(CO)NO}PPh2. This reactive intermediate, however, can be methylated by MeI and CF3SO3Me or organometallated by C5H5Fe(CO)(2)Cl to yield the phosphonium salts [{Cp'Mn(CO)NO}PPh2Me]PF6 and [{Cp'Mn(CO)NO}PPh2{C5H5Fe(CO)(2)}]PF6, respectively. The methyl derivative is deprotonated by (BuLi)-Bu-n to give the unstable methylene phosphorane {Cp'Mn(CO)NO}PPh2=CH2, an organometallated phosphorus ylide. The in situ from [{Cp'Mn(CO)NO}PPh2H]BF4 generated phosphane [Cp'Mn(CO)NO}PPh2 is oxidized by epoxycyclohexane to give the intermediate oxophosphorane {Cp'Mn(CO)NO}P(O)Ph-2, which reacts with the still available starting material to yield the first dimanganiodiphenylphosphonium salt [{Cp'Mn(CO)NO}(2)PPh2]BF4. The compounds have been characterized by spectroscopic (IR, NMR, MS), analytical (C, H, N) and X-ray diffraction investigations ([{C5H5Mn(CO)NO}PPh2H]BF4, [{Cp'Mn(CO)NO}PPh2Me]BF6, [{Cp'Mn(CO)NO)(2)PPh2]-BF4). [References: 28]