Reactions of trialkoxynitridomolybdenum with low-coordinate phosphorus compounds containing a PN double bond

Abstract

The reactions of NMo(OR)₃ (R = ^tBu, ⁱPr) with (Me₃Si)₂NPNSiMe₃ (1), (Me₃Si)₂NPN^tBu (2), (Me₃Si)₂NPS(N^tBu) (3) and (Me₃Si)₂NP(NSiMe₃)₂ (4) have been studied. Reported complexes were synthesized via1,2-addition of an Mo–OR bond across the PN bond, resulting in four-membered metallacycles of the corresponding σ²λ³-iminophosphine or σ³λ⁵-iminophosphorane with trialkoxynitridomolybdenum. The structure of all new compounds was elucidated by ¹H, ¹³C and ³¹P NMR spectroscopy. Compounds [(Me₃Si)₂N–P(NSiMe₃)(O–^tBu)]{(^tBuO)₂MoN} (5), [(Me₃Si)₂N–PS(N^tBu)(O–^tBu)]{(^tBuO)₂MoN} (7), [(Me₃Si)₂N–P(NSiMe₃)₂(O–^tBu)]{(^tBuO)₂MoN} (8) and [(Me₃Si)₂N–P(NSiMe₃)₂(O–ⁱPr)]{(ⁱPrO)₂MoN} (12) were also characterized by single X-ray analysis and shown to be metallacycles containing the Mo atom with an intact terminal nitrido ligand.