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Thorium Metallocene Cation Chemistry: Synthesis and Characterization of the Bent [(C5Me5)2Th(C6H5)(THF)][BPh4] and the Parallel Ring [(C5Me5)2Th(NCR)5][BPh4]2 (R = Me, Ph) Complexes

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journal contribution
posted on 31.01.2018, 14:11 by Ryan R. Langeslay, Cory J. Windorff, Megan T. Dumas, Joseph W. Ziller, William J. Evans
Attempts to synthesize the base-free dication [(C5Me5)2Th]2+ by reaction of the bis­(allyl) complex (C5Me5)2Th­(C3H5)2 with 2 equiv of [Et3NH]­[BPh4] in benzene yielded a cationic phenyl complex that, in the presence of THF, crystallized from toluene as [(C5Me5)2Th­(C6H5)­(THF)]­[BPh4]. The reaction of the dimethyl complex (C5Me5)2ThMe2 with [Et3NH]­[BPh4] in toluene in the presence of nitriles RCN generates cations of the formula [(C5Me5)2Th­(NCR)5]­[BPh4]2 (R = Me, Ph) in 40–55% crystalline yield. The molecular structures reveal the first examples of thorium cyclopentadienyl metallocene complexes with parallel rings.