Reactions of N≡W(O^tBu)₃ and O=W(OⁱPr)₄ with Low-Coordinate Phosphorus Compounds: Similarities and Differences

Abstract

The reactions of N≡W(O^tBu)₃ and O=W(OⁱPr)₄ with (Me₃Si)₂NPNSiMe₃ (I), (Me₃Si)₂NPN^tBu (II), and (Me₃Si)₂NP(NSiMe₃)₂ (III) in benzene have been studied. Low-coordinate phosphorus derivatives react with above mentioned tungsten compounds via 1,2-addition of an W-OR bond across the P=N bond, resulting in four-membered metallacycles. (Me₃Si)₂N-P(NSiMe₃)₂ reacts with O=W(OⁱPr)₄ in a different manner via [2 + 2] cycloaddition. The structure of all new compounds was elucidated by ¹H, ¹³C, and ³¹P NMR spectroscopy. Compound [(Me₃Si)₂N-P(NSiMe₃)₂(O)]{W(OⁱPr)₄} (6) was also characterized by single crystal X-ray analysis.

Keywords:

• Crystal structure
• low-coordinate phosphorus
• metallacycle
• tungsten