A family of group 6 transition metal complexes M(C5R5)(CO)2(CF) [M = Cr, Mo, W; R = H, Me] with terminal fluoromethylidyne ligands have been synthesized through the reduction of the corresponding trifluoromethyl precursors with potassium graphite or magnesium graphite. They have been characterized spectroscopically and in some cases crystallographically, although the structures show disorder between the CO and CF ligands. The MCF subunit reacts as a triple bond to form cluster complexes containing μ3-CF ligands on reaction with Co2(CO)8. Computational (DFT/NBO/NRT) studies on M(C5H5)(CO)2(CF) [M = Cr, Mo, W] and the corresponding cationic fragments M(CO)2(XY)+ illustrate significant differences in the metal–ligand bonding between CF and its isoelectronic analogue NO, as well as with its hydrocarbon analogue CH.
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