Substituted 1,4-Diaza-1,3-butadiene Monocyclopentadienyl Titanium Complexes. Crystal Structure of Ti(η5-C5Me5)(η4-iPrNCHCHNiPr)Me

We report the synthesis of 1,4-diaza-1,3-butadiene (dad) complexes Ti(η5-C5R5)(η4-R‘2-dad)Cl (R = H, Me; R‘ = iPr, tBu) by reaction of Ti(η5-C5R5)Cl3 (R = H, Me) with the dilithium salts of diisopropyl- and di-tert-butyl-substituted 1,4-diaza-1,3-butadienes (Li2[R‘2-dad]). Alkylation of the pentamethylcyclopentadienyl diisopropyl and di-tert-butyl derivatives with methylmagnesium chloride and methyllithium gave complexes Ti(η5-C5Me5)(η4-iPr2-dad)Me and Ti(η5-C5Me5)(η4-tBu2-dad)Me, respectively. Addition of excess water to di-tert-butyl chloro complexes gave the oxo-bridged complexes [{Ti(η5-C5R5)(η4-tBu2-dad)}2(μ-O)] (R = H, Me). The temperature-dependent spectroscopic behavior of Ti(η5-C5H…