Reactivity of the tethered alkyl uranium bonds of (η5:κ1-C5Me4SiMe2CH2)2U

Abstract

Uranium-carbon bond reactivity has been investigated with the bis(tethered silylalkyl) uranium metallocene ( η 5 : κ 1 -C 5 Me 4 SiMe 2 CH 2 ) 2 U, 1 . Tert -butyl nitrile, t BuC N, inserts into both of the tethered U-C bonds to produce the bis(tethered ketimide) complex [ η 5 : κ 1 -C 5 Me 4 SiMe 2 CH 2 C( t Bu)N] 2 U, 2 , which has unusually bent U-N-C bond angles. Carbon dioxide also inserts into both U-C bonds of 1 yielding the bis(tethered carboxylate) (C 5 Me 4 SiMe 2 CH 2 CO 2 ) 2 U, 3 . Neither PhC CPh nor PhC CH insert into the U-C bonds, but PhC CH cleaves the silylalkyl tethers in 1 to generate (C 5 Me 4 SiMe 3 ) 1− ligands in the complex (C 5 Me 4 SiMe 3 ) 2 U(C CPh) 2 , 4 .