Synthesis and Reactivity of d0Alkyl, Silyl, and Hydride Complexes of Titanium and Zirconium Featuring an Aryl-Substituted Tripodal Triamido Ligand Derived fromcis,cis-1,3,5-Triaminocyclohexane

Abstract

Zirconium and titanium complexes containing the new chelating triamido ligand [cis,cis-1,3,5-(3,5-tBu2C6H3N)3C6H9]3- (1) are reported. The chloride complexes [cis,cis-1,3,5-(3,5-tBu2C6H3N)3C6H9]TiCl (2) and [cis,cis-1,3,5-(3,5-tBu2C6H3N)3C6H9]ZrCl (3) were prepared by reaction of TiCl4(THF)2 and ZrCl4, respectively, with [1]Li3 (prepared in situ). The diethyl ether adduct of 3 (3·OEt2) was crystallographically characterized. The alkyl complexes [cis,cis-1,3,5-(3,5-tBu2C6H3N)3C6H9]ZrCH2SiMe3 (4) and [cis,cis-1,3,5-(3,5-tBu2C6H3N)3C6H9]ZrCH2Ph (5) were prepared by reaction of the triamine ([1]H3) with Zr(CH2SiMe3)4 and Zr(CH2Ph)4, respectively. The aryl complexes [cis,cis-1,3,5-(3,5-tBu2C6H3N)3C6H9]ZrPh (6) and [cis,cis-1,3,5-(3,5-tBu2C6H3N)3C6H9]ZrMes (7, Mes = 2,4,6-Me3C6H2) were prepared by the reaction of 3 with PhLi and MesLi, respectively. Similarly, [cis,cis-1,3,5-(3,5-tBu2C6H3N)3C6H9]TiMe (8) was prepared by the reaction of 2 with MeMgBr. The alkyl and aryl complexes 4−8 did not react with hydrosila...