Reactivity of the Donor‐Stabilized Silylenes [ i PrNC(Ph)N i Pr] 2 Si and [ i PrNC(N i Pr 2 )N i Pr] 2 Si: Activation of CO 2 and CS 2

Activation of CO 2 by the bis(amidinato)silylene 1 and the analogous bis(guanidinato)silylene 2 leads to the structurally analogous six‐coordinate silicon( IV ) complexes 4 (previous work) and 8 , respectively, the first silicon compounds with a chelating carbonato ligand. Likewise, CS 2 activation by silylene 1 affords the analogous six‐coordinate silicon( IV ) complex 10 , the first silicon compound with a chelating trithiocarbonato ligand. CS 2 activation by silylene 2 , however, yields the five‐coordinate silicon( IV ) complex 13 with a carbon‐bound CS 2 2− ligand, which also represents an unprecedented coordination mode in silicon coordination chemistry. Treatment of the dinuclear silicon( IV ) complexes 5 and 6 with CO 2 also affords the six‐coordinate carbonatosilicon( IV ) complexes 4 and 8 , respectively.