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

The Lewis base supported thorium terminal imido metallocene (eta(5)-C5Me5)(2)Th=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 (eta(5)-C5Me5)(2)Th=N(mesityl)(OPPh3) (2) with Ph3PO, deprotonation occurs between 1 and thiazole to give the amido thiazolyl complex (eta(5)- VC5Me5)(2)Th(NHmesityl)(C3H2NS) (3). Moreover, the five-membered metallaheterocycle (eta(5)-C5Me5)(2)Th[kappa(2)-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 (eta(5)-C5Me5)(2)Th[kappa-N-{NCPh(N(mesityl))}](DMAP) (5), and iminato compounds (eta(5)-C5Me5)(2)Th[N(mesityl)C(CHPh2)NH](N=C=CPh2) (6) and (eta(5)-C5Me5)2Th[2-{N=C(SiMe3)}-4-Me2NC5H3N](NC) (7), respectively. Furthermore, reaction of 1 with PhC equivalent to CMe and Me3SiC equivalent to CC equivalent to CSiMe3 afford the amido pyridyl complexes (eta(5)-C5Me5)(2)Th[N(mesityl)C(Me)=CHPh](kappa(2)-C,N-4-Me2NC5H3N) (8) and (eta(5)-C5Me5)2Th[N(mesityl)C(C2SiMe3)=CHSiMe3](kappa(2)-C,N-4-Me2NC5H3N) (9), respectively. Treatment of 1 with N,N'-diisopropylcarbodiimide furnishes the [2 + 2] cycloaddition product (eta(5)-C5Me5)(2)Th[N(mesityl)C(=(NPr)-Pr-i)-(NPr)-Pr-i](DMAP) (10), whereas reaction of 1 with CS2 or PhNCS affords the four-membered metallaheterocycles (eta(5)-C5Me5)(2)Th[SC=N(mesityl)-S](DMAP) (11) and (eta(5)-C5Me5)(2)Th[SC=N(mesityl)-NPh](DMAP) (12), respectively. Moreover, while the four-membered metallaheterocycle (eta(5)-C5Me5)(2)Th[(mu-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 (eta(5)-C5Me5)(2)Th(NH(mesityl))(kappa-O-1-OC9H7) (14). Nevertheless, the eight-membered metallaheterocycle (eta(5)-C5Me5)(2)Th[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)N-3 affords the tetraazametallacyclopentene (eta(5)-C5Me5)(2)Th[N(p-tolyl)N=NN(p-tolyl)] (16), reaction of 1 with Me3SiCHN2 forms the bimetallic complex [(eta(5)-C5Me5)(2)Th]2(mu-N=NN=CSiMe3)(2) (17) concomitant with the elimination of mesitylene. The new complexes 215 and 17 were characterized by various spectroscopic techniques, including single-crystal X-ray diffraction studies.