Extracting absolute titanium-alkyl and-hydride bond enthalpies from relative D(TiR(H)) in (silox)2(tBu3SiNH)TiR: electronegativity and ECT models

Relative D(Ti-R)rel have been measured previously for (silox)2(tBu3SiNH)TiR (1-R). Pauling and Matcha equations of D(MR) that contain elements of electronegativity, D(MM), D(HH) and D(RH) were used to estimate absolute D(TiR) in 1 with minimal success. The electronegativity approaches need a variety of substituents with a wide spread in χR, hence examination of 1-H and 1-R are heavily and incorrectly weighted by D(TiH)-D(TiR). Absolute D(TiR) generated in this manner approach those of related systems only when χXTi = 2.9, a value shown to be irrational. Drago's ECT parameters were used in the hope that the three parameter fit would compensate for inadequacies in electronegativity-based methods. The limited set of alkyl parameters available, and a lack of distinguishing parameters that can significantly differentiate one alkyl from another, render this potentially useful method imprecise.