ja036559r_si_004.txt (30.79 kB)

Four-Coordinate Phosphinidene Complexes of Titanium Prepared by α-H-Migration:  Phospha-Staudinger and Phosphaalkene-Insertion Reactions

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posted on 05.08.2003, 00:00 by Falguni Basuli, John Tomaszewski, John C. Huffman, Daniel J. Mindiola
α-Hydrogen migration in the phosphide (Nacnac)TiCHtBu(PHR) (Nacnac- = [Ar]NC(Me)CHC(Me)N[Ar], Ar = 2,6-iPr2C6H3, R = C6H11, 2,4,6-iPr3C6H2, 2,4,6-tBuC6H2), prepared from salt metathesis of (Nacnac)TiCHtBu(PHR) with LiPHR, generates terminal and four-coordinate phosphinidene complexes (Nacnac)TiPR(CH2tBu), one of which was structurally characterized (R = 2,4,6-tBu3C6H2). Phosphinidene intermediate (Nacnac)TiPR(CH2tBu) (R = C6H11, 2,4,6-iPr3C6H2) transform to ([Ar]NC(Me)CHC(Me)P[R][CH2tBu])TiNAr(OEt2) through “phospha-Staudinger” and subsequent phosphaalkene-insertion reactions.

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