title: Formation of the imide [Ta(NMe2)3(μ-NSiMe3)]2 through an unprecedented α-SiMe3 abstraction by an amide ligand.
abstract: Ta(NMe(2))(4)[N(SiMe(3))(2)] (1) undergoes the elimination of Me(3)Si-NMe(2) (2), converting the -N(SiMe(3))(2) ligand to the ═NSiMe(3) ligand, to give the imide "Ta(NMe(2))(3)(═NSiMe(3))" (3) observed as its dimer 4. CyN═C═NCy captures 3 to yield guanidinates Ta(NMe(2))(3-n)(═NSiMe(3))[CyNC(NMe(2))NCy](n) [n = 1 (5), 2 (6)]. The kinetic study of α-SiMe(3) abstraction in 1 gives ΔH(‡) = 21.3(1.0) kcal/mol and ΔS(‡) = -17(2) eu.
authors.affiliation: Department of Chemistry, The University of Tennessee, Knoxville, Tennessee 37996, USA.
authors.forename: Bhavna
authors.initials: B
authors.lastname: Sharma
authors.forename: Shu-Jian
authors.initials: SJ
authors.lastname: Chen
authors.forename: Julia K C
authors.initials: JK
authors.lastname: Abbott
authors.forename: Xue-Tai
authors.initials: XT
authors.lastname: Chen
authors.forename: Zi-Ling
authors.initials: ZL
authors.lastname: Xue