An Entry to Mixed NHC-Fischer Carbene Complexes and Zwitterionic Group 6 Metal Alkenyls

The addition of NHCs to ,-unsaturated Cr-0 and W-0 (Fischer) carbene complexes is strongly dependent on the electrophilicity of the carbene carbon. Electrophilic alkoxy-carbene complexes quantitatively react with NHCs to yield stable zwitterionic (racemic) Cr-0- and W-0-alkenyls with total regio- and E-stereoselectivity. Less electrophilic aminocarbenes react with NHCs to promote the displacement of a CO ligand and yield mixed NHC/Fischer biscarbenes in a process that is unprecedented in group 6 metal-carbene chemistry. In fact, the compounds prepared, are some of the scarce examples of Fischer bisylidenes reported in the literature. The electrochemistry of the zwitterionic Cr-0- and W-0-alkenylcomplexes made, show that these compounds have a strong reductor character, which is demonstrated in their reactions towards [Ph3C][PF6]. The oxidation processes lead to new types of cationic Fischer mono- and biscarbene complexes having a charged NHC fragment in their structures, in a new example of the use of electron-transfer reactions as a method to prepare novel group 6 (Fischer) carbene complexes.