Abstract
Addition of 2.0 equiv of Na(silox) to TiCl4(THF)2 afforded (silox)2TiCl2 (1), which yielded (silox)2(tBu3SiNH)TiCl (2-Cl) upon treatment with tBu3SiNLi. Grignard or alkyllithium additions to 2-Cl or 1,2-RH-addition to transient (silox)2TiNSitBu3 (3) produced (silox)2(tBu3SiNH)TiR (2-R; R = Me, Et, CH2Ph = Bz, CHCH2 = Vy, cBu, nBu, Ph, H, cPr, cPe, CH2-3,5-Me2C6H3 = Mes, neoHex, cHex, η3-H2CHCH2, η3-H2CCHCHMe). Insertions of C2H4, butadiene, HC2H, and HC2tBu into the titanium−hydride bond of 2-H generated (silox)2(tBu3SiNH)TiR (2-R; R = Et, η3-H2CCHCHMe, Vy, E-CHCHtBu). Trapping of 3 by donors L afforded (silox)2LTiNSitBu3 (3-L; L = OEt2, THF (X-ray, two independent molecules: d(TiN) = 1.772(3), 1.783(3) A), py, PMe3, NMe3, NEt3) and RC2R‘ = HC2H, MeC2Me, EtC2Et, HC2tBu) and Kinetics of 1,2-RH-elimination from 2-R revealed a first-order process (24.8 °C): R = Bz < Mes < H < Me (1.54(10) × 10-5 s-1) < neoHex < Et < nBu < cBu < cPe < cHex < cPr < Vy < Ph. Kinetics data, large 1,2-RH/D-elimination KIE's (e....
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