Reactivity and electronic property of decaphenylmetallocenes of Mo and W atoms

The perphenylmetallocene complexes (η5-C5Ph5)2W (1), [(η5-C5Ph5)2W]+I3− (1+I3), (η5-C5Ph5)2Mo (2) and [(η5-C5Ph5)2Mo]+I3− (2+I3) have been prepared. Hydrogenation of 1 in THF produces (η5-C5Ph5)2WH2 (4), while (η5-C5Ph5)2WHCl (3) is afforded in 1,2-dichloroethane solvent. Carbonylation of 1 produces (η5-C5Ph5)2W(CO) (5). Treatment of 1 with the strong acid CF3SO3H leads to the dicationic species [(η5-C5Ph5)2W]+2[CF3SO3]−2 (1+2Tf2) after crystallization. The structures of 2+I3 and 1+2Tf2 have been determined by an X-ray diffraction study. The magnetic susceptibility study indicates a 3E2g ground-state for 1 and 2, and a 4A2g ground-state for 1+ and 2+.