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Masuda JD, Hoskin AJ, Graham TW, et al. Catalytic P--H activation by Ti and Zr catalysts. Chemistry. 2006;12(34):8696-707doi: 10.1002/chem.200600429.
Masuda, J. D., Hoskin, A. J., Graham, T. W., Beddie, C., Fermin, M. C., Etkin, N., & Stephan, D. W. (2006). Catalytic P--H activation by Ti and Zr catalysts. Chemistry (Weinheim an der Bergstrasse, Germany), 12(34), 8696-707. https://doi.org/10.1002/chem.200600429
Masuda, Jason D, et al. "Catalytic P--H activation by Ti and Zr catalysts." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 12,34 (2006): 8696-707. doi: https://doi.org/10.1002/chem.200600429
Masuda JD, Hoskin AJ, Graham TW, Beddie C, Fermin MC, Etkin N, Stephan DW. Catalytic P--H activation by Ti and Zr catalysts. Chemistry. 2006 Nov 24;12(34):8696-707. doi: 10.1002/chem.200600429. PMID: 16952126.
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Chemistry. 2006 Nov 24;12(34):8696-707. doi: 10.1002/chem.200600429.

Catalytic P--H activation by Ti and Zr catalysts.

Chemistry (Weinheim an der Bergstrasse, Germany)

Jason D Masuda, Aaron J Hoskin, Todd W Graham, Chad Beddie, Maria C Fermin, Nola Etkin, Douglas W Stephan

Affiliations

  1. Department of Chemistry & Biochemistry, University of Windsor, Windsor, Ontario N9B 3P4, Canada.

PMID: 16952126 DOI: 10.1002/chem.200600429

Abstract

Catalytic dehydrocoupling of phosphines was investigated using the anionic zirconocene trihydride salts [Cp*2Zr(mu-H)3Li]3 (1 a) or [Cp*2Zr(mu-H)3K(thf)4] (1 b), and the metallocycles [CpTi(NPtBu3)(CH2)4] (6) and [Cp*M(NPtBu3)(CH2)4] (M=Ti 20, Zr 21) as catalyst precursors. Dehydrocoupling of primary phosphines RPH2 (R=Ph, C6H2Me3, Cy, C10H7) gave both dehydrocoupled dimers RP(H)P(H)R or cyclic oligophosphines (RP)n (n=4, 5) while reaction of tBu3C6H2PH2 gave the phosphaindoline tBu2(Me2CCH2)C6H2PH 9. Stoichiometric reactions of these catalyst precursors with primary phosphines afforded [Cp*2Zr((PR)2)H][K(thf)4] (R=Ph 2, Cy 3, C6H2Me3 4), [Cp*2Zr((PPh)3)H][K(thf)4] (5), [CpTi(NPtBu3)(PPh)3] (7) and [CpTi(NPtBu3)(mu-PHPh)]2 (8), while reaction of 6 with (C6H2tBu3)PH2 in the presence of PMe3 afforded [CpTi(NPtBu3)(PMe3)(P(C6H2tBu3)] (10). The secondary phosphines Ph2PH and (PhHPCH2)2CH2 also undergo dehydrocoupling affording (Ph2P)2 and (PhPCH2)2CH2. The bisphosphines (CH2PH2)2 and C6H4(PH2)2 are dehydrocoupled to give (PCH2CH2PH)2)(12) and (C6H4P(PH))2 (13) while prolonged reaction of 13 gave (C6H4P2)(8) (14). The analogous bisphosphine Me2C6H4(PH)2 (17) was prepared and dehydrocoupling catalysis afforded (Me2C6H2P(PH))2 (18) and subsequently [(Me2C6H2P2)2(mu-Me2C6H2P2)]2 (19). Stoichiometric reactions with these bisphosphines gave [Cp*2Zr(H)(PH)2C6-H4][Li(thf)4] (22), [CpTi(NPtBu3)(PH)2C6H4]2 (23) and [Cp*Ti(NPtBu3)(PH)2C6H4] (24). Mechanistic implications are discussed.

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