5 years ago

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

Reactivity of a Lewis Base Supported Thorium Terminal Imido Metallocene toward Small Organic Molecules
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 215 and 17 were characterized by various spectroscopic techniques, including single-crystal X-ray diffraction studies.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00212

DOI: 10.1021/acs.organomet.7b00212

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