N-Heterocyclic Silylenes as Ligands in Transition Metal Carbonyl Chemistry: Nature of Their Bonding and Supposed Innocence

A study on the reactivity of the N-heterocyclic silylene Dipp₂NHSi (1,3-bis(diisopropylphenyl)-1,3-diaza-2-silacyclopent-4-en-2-yliden) with the transition metal complexes Ni(CO)₄], M(CO)₆] (M=Cr, Mo, W), Mn(CO)₅(Br)] and (η⁵-C₅H₅)Fe(CO)₂(I)] is reported. We demonstrate that N-heterocyclic silylenes, the higher homologues of the now ubiquitous NHC ligands, show a remarkably different behavior in coordination chemistry compared to NHC ligands. Calculations on the electronic features of these ligands revealed significant differences in the frontier orbital region which lead to some peculiarities of the coordination chemistry of silylenes, as demonstrated by the synthesis of the dinuclear, NHSi-bridged complex {Ni(CO)₂(μ-Dipp₂NHSi)}₂] ( 2 ), complexes M(CO)₅(Dipp₂NHSi)] (M=Cr 3 , Mo 4 , W 5 ), Mn(CO)₃(Dipp₂NHSi)₂(Br)] ( 9 ) and (η⁵-C₅H₅)Fe(CO)₂(Dipp₂NHSi-I)] ( 10 ). DFT calculations on several model systems Ni(L)], Ni(CO)₃(L)], and W(CO)₅(L)] (L=NHC, NHSi) reveal that carbenes are typically the much better donor ligands with a larger intrinsic strength of the metal–ligand bond. The decrease going from the carbene to the silylene ligand is mainly caused by favorable electrostatic contributions for the NHC ligand to the total bond strength, whereas the orbital interactions were often found to be higher for the silylene complexes. Furthermore, we have demonstrated that the contribution of σ- and π-interaction depends significantly on the system under investigation. The σ-interaction is often much weaker for the NHSi ligand compared to NHC but, interestingly, the π-interaction prevails for many NHSi complexes. For the carbonyl complexes, the NHSi ligand is the better σ-donor ligand, and contributions of π-symmetry play only a minor role for the NHC and NHSi co-ligands.