Cycloaddition Reactions of the Titanium Imide [Ti(NBu^t){MeC(2-C₅H₄N)(CH₂NSiMe₃)₂}(py)] with Bu^tCP and MeCN

Abstract

The diamidopyridine-supported titanium imide [Ti(NBu t )(L)(py)] [ 1, L = MeC(2- C 5 H 4 N)(CH 2 NSiMe 3 ) 2 ] undergoes a [2+2] cycloaddition reaction with Bu t CP to form the mononuclear product [Ti{N(Bu t )PC(Bu t )}(L)] ( 2 ). In contrast, reaction of 1 with MeCN affords the binuclear derivative [Ti 2 {μ-η 2 -NC(Me)NBu t } 2 (L) 2 ] ( 3 ), which contains a doubly deprotonated N - tert -butylacetamidinate ligand. Compound 3 undergoes a quantitative cycloreversion reaction at elevated temperatures yielding MeCN and [Ti(NBu t )(L)] ( 4 ).