Complexes of Trivalent Phosphorus Derivatives Viii. Tris (Dimethylamino) Phosphine Complexes of Manganese Carbonyl.

摘要

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. 198-199C. Reduction of this compound with dilute sodium amalgam in tetrahydrofuran 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)3-SnMn(CO)4Tdp with a manganese-tin sigma-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). Reaction of Na(Mn(CO)4Tdp) with excess tert-butyl chloride and N-methyl-N-nitroso-p-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. (Author)