PREPARATION AND PROPERTIES OF MOLYBDENUM AND TUNGSTEN DINITROGEN COMPLEXES .32. A SERIES OF NOVEL CARBONYL-COMPLEXES OF TUNGSTEN DERIVED FROM THE DINITROGEN COMPLEX TRANS-[W(N2)2(PH2PCH2CH2PPH2)2]

Treatment of trans-[W(N2)2(dppe)2] (dppe=Ph2PCH2CH2PPh2) with N,N-dimethylformamide (DMF) in benzene under reflux afforded trans-[W(CO)(DMF)(dppe)2], together with a hydridocarbamoyl complex [WH(eta-2-CONMe2)(dppe)2] as the intermediate stage of this decarbonylation reaction. The detailed structure of the latter complex was determined by X-ray crystallography. Reaction of trans-[W(CO)(DMF)(dppe)2] with N2 afforded trans-[W(CO)(N2)(dppe)2], whose solution in benzene was further converted into a coordinatively unsaturated complex [W(CO)(dppe)2] under reflux in an Ar atmosphere. Subsequent treatment of [W(CO)(dppe)2] with H2 gas gave a dihydrido complex [WH2(CO)(dppe)2].