COMPLEXES OF TRIVALENT PHOSPHORUS DERIVATIVES .8. TRIS(DIMETHYLAMINO)PHOSPHINE COMPLEXES OF MANGANESE CARBONYL

Tris(dimethylamino)phosphine (Tdp) reacts with Mn2(CO)10 in a boiling mixture of 2,2,5-trimethylhexane and toluene to give yellow [TdpMn(CO)4]2, m.p. 198-199°. Reduction of this compound with dilute sodium amalgam in tetra hydrofuran gives a solution of the sodium salt Na[Mn(CO)4Tdp] which reacts with alkyl halides to give the stable white cis-RMn(CO)4Tdp(R = methyl or benzyl)derivatives. Reaction of Na[Mn(CO)4Tdp] with trimethyltin chloride gives white cis-(CH3)3SnMn(CO)4Tdp with a manganesetin σ-bond. Treatment of [TdpMn(CO)4]2 with the halogens X2(X = Br or I) in dichloromethane solution at room temperature gives the yellow halides cis-TdpMn(CO)4X (X = Br or I). The iodide was alsoobtained from Na[Mn(CO)4Tdp] and C3F7I. Reaction of Na[Mn(CO)4Tdp] with excess tert-butyl chloride and N-methyl-N-nitroso-π-toluenesulfonamide (Diazald) gives the red crystalline carbonyl nitrosyl TdpMn(CO)3NO. Treatment of [TdpMn(CO)4]2 with excess nitric oxide gives the green volatile unstable trinitrosyl TdpMn(NO)3. The infrared and proton NMR spectra of the new compounds are discussed. © 1969.