Abstract
The N-heterocyclic silylene [{Fe(η(5) -C(5) H(4) -NDipp)(2) }Si] (1DippSi, Dipp=2,6-diisopropylphenyl) shows an excellent combination of pronounced thermal stability and high reactivity towards small molecules. It reacts readily with CO(2) and N(2) O, respectively affording (1DippSiO(2) )(2) C and (1DippSiO)(2) as follow-up products of the silanone 1DippSiO. Its reactions with H(2) O, NH(3) , and FcPH(2) (Fc=ferrocenyl) furnish the respective oxidative addition products 1DippSi(H)X (X=OH, NH(2) , PHFc). Its reaction with H(3) BNH(3) unexpectedly results in B-H, instead of N-H, bond activation, affording 1DippSi(H)(BH(2) NH(3) ). DFT results suggest that dramatically different mechanisms are operative for these H-X insertions.