Multimetal Fischer carbene complexes of Group VI transition metals: synthesis, structure and substituent effect...

Fischer carbene complexes of tungsten with substituents containing up to two additional different transition metals, with all the metals in electronic contact with the carbene carbon atom, were synthesised and studied both in solution and in the solid state. For the complexes of the type [W(CO)(5){C(OR')R}], the substituents chosen were heteroaromatic 2-benzo[b]thienyl (2-BT), or 2-BT π-bonded to a chromium tricarbonyl fragment ([Cr(CO)(3)(2-η(6)-BT)]) or ferrocenyl (Fc) as the R-substituent, while the OR'-substituent was systematically varied between an ethoxy or a titanoxy group, to yield the complexes 1b (R' = Et, R = 2-BT), 2b (R' = Et, R = [Cr(CO)(3)(2-η(6)-BT)]), 3b (R' = TiCp(2)Cl, R = 21-BT), 4b (R' = TiCp(2)Cl, R = [Cr(CO)(3)(2-η(6)-BT)]), 5b (R' = Et, R = Fc) and 6b (R' = TiCp(2)Cl, R = Fc). The structural features and their relevance to bonding in the multimetal carbene compounds of both these tungsten and the analogous chromium complexes were investigated as they represent indicators of possible reactivity sites in multimetal carbene assemblies. The possibility of using DFT calculations to quantify the effect of metal-containing substituents on the carbene ligands was tested and correlated with experimental parameters by employing methods such as vibrational spectroscopy, molecular orbital analysis, and cyclic voltammetry.