Reactivity of a Lewis Base Supported Thorium Terminal Imido Metallocene toward Small Organic Molecules

The Lewis base supported thorium terminal imido metallocene (η5-C5Me5)2Th═N(mesityl)(DMAP) (1) reacts with various small organic molecules such as thiazoles, silanes, internal acetylenes, nitriles, ketones, CS2, isothiocyanates, carbodiimides, lactides, organic azides, and diazoalkane derivatives. For example, while 1 forms the adduct (η5-C5Me5)2Th═N(mesityl)(OPPh3) (2) with Ph3PO, deprotonation occurs between 1 and thiazole to give the amido thiazolyl complex (η5-C5Me5)2Th(NHmesityl)(C3H2NS) (3). Moreover, the five-membered metallaheterocycle (η5-C5Me5)2Th[κ2-N,C-{N(2-CH2-4,6-Me2C6H2)(SiH2Ph)}](DMAP) (4) is isolated from a mixture of 1 and PhSiH3. In addition, treatment of 1 with PhCN, Ph2CHCN, or Me3SiCN gives the zwitterionic complex (η5-C5Me5)2Th[κ-N-{NCPh(N(mesityl))}](DMAP) (5), and iminato compounds (η5-C5Me5)2Th[N(mesityl)C(CHPh2)NH](N═C═CPh2) (6) and (η5-C5Me5)2Th[2-{N═C(SiMe3)}-4-Me2NC5H3N](NC) (7), respectively. Furthermore, reaction of 1 with PhC≡CMe and Me3SiC≡CC≡CSiMe3 afford the amido pyrid...