Marc D. Walter, Enwei Zhou, Pikun Yang, Congcong Zhang, Xuebin Deng, Guofu Zi
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 pyridyl complexes (η5-C5Me5)2Th[N(mesityl)C(Me)═CHPh](κ2-C,N-4-Me2NC5H3N) (8) and (η5-C5Me5)2Th[N(mesityl)C(C2SiMe3)═CHSiMe3](κ2-C,N-4-Me2NC5H3N) (9), respectively. Treatment of 1 with N,N′-diisopropylcarbodiimide furnishes the [2 + 2] cycloaddition product (η5-C5Me5)2Th[N(mesityl)C(═NiPr)-NiPr](DMAP) (10), whereas reaction of 1 with CS2 or PhNCS affords the four-membered metallaheterocycles (η5-C5Me5)2Th[SC═N(mesityl)-S](DMAP) (11) and (η5-C5Me5)2Th[SC═N(mesityl)-NPh](DMAP) (12), respectively. Moreover, while the four-membered metallaheterocycle (η5-C5Me5)2Th[(μ-O)2(CPh2)](DMAP) (13) is formed upon addition of Ph2CO to 1, deprotonation occurs between 1 and 1-indanone to give the amido enolyl compound (η5-C5Me5)2Th(NH(mesityl))(κ-O-1-OC9H7) (14). Nevertheless, the eight-membered metallaheterocycle (η5-C5Me5)2Th[OCH(Me)C(═O)OCH(Me)C(═N(mesityl))O] (15) is isolated from reaction of 1 with rac-lactide. Furthermore, while mixing 1 with (p-tolyl)N3 affords the tetraazametallacyclopentene (η5-C5Me5)2Th[N(p-tolyl)N═NN(p-tolyl)] (16), reaction of 1 with Me3SiCHN2 forms the bimetallic complex [(η5-C5Me5)2Th]2(μ-N═NN═CSiMe3)2 (17) concomitant with the elimination of mesitylene. The new complexes 2–15 and 17 were characterized by various spectroscopic techniques, including single-crystal X-ray diffraction studies.
