Reactions of trialkoxynitridomolybdenum with low-coordinate phosphorus compounds containing a P=N double bond

The reactions of N≡Mo(OR)(3) (R = (t)Bu, (i)Pr) with (Me(3)Si)(2)NPNSiMe(3) (1), (Me(3)Si)(2)NPN(t)Bu (2), (Me(3)Si)(2)NPS(N(t)Bu) (3) and (Me(3)Si)(2)NP(NSiMe(3))(2) (4) have been studied. Reported complexes were synthesized via 1,2-addition of an Mo-OR bond across the P=N bond, resulting in four-membered metallacycles of the corresponding σ(2)λ(3)-iminophosphine or σ(3)λ(5)-iminophosphorane with trialkoxynitridomolybdenum. The structure of all new compounds was elucidated by (1)H, (13)C and (31)P NMR spectroscopy. Compounds [(Me(3)Si)(2)N-P(NSiMe(3))(O-(t)Bu)]{((t)BuO)(2)Mo≡N} (5), [(Me(3)Si)(2)N-PS(N(t)Bu)(O-(t)Bu)]{((t)BuO)(2)Mo≡N} (7), [(Me(3)Si)(2)N-P(NSiMe(3))(2)(O-(t)Bu)]{((t)BuO)(2)Mo≡N} (8) and [(Me(3)Si)(2)N-P(NSiMe(3))(2)(O-(i)Pr)]{((i)PrO)(2)Mo≡N} (12) were also characterized by single X-ray analysis and shown to be metallacycles containing the Mo atom with an intact terminal nitrido ligand.