Catalytic P-H activation by Ti and Zr catalysts

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Title Catalytic P-H activation by Ti and Zr catalysts
Author(s) J. D. Masuda, A. J. Hoskin, T. W. Graham, C. Beddie, M. C. Fermin, Nola Etkin, D. W. Stephan
Journal Chemistry-a European Journal
Date 2006
Volume 12
Issue 34
Start page 8696
End page 8707
Abstract Catalytic dehydrocoupling of phosphines was investigated using the anionic zirconocene trihydride salts [Cp*Zr-2(mu-H)(3)Li](3) (1a) or [Cp*Zr-2(mu-H)(3)K(thf)(4)] (1b), 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 tBu(3)C(6)H(2)PH(2) gave the phosphaindoline tBu(2)(Me2CCH2)C6H2PH (9). Stoichiometric reactions of these catalyst precursors with primary phosphines afforded [Cp*Zr-2((PR)(2))H][K(thf)(4)] (R = Ph 2, Cy 3, C6H2Me3 4), [Cp*Zr-2((PPh)(3))H] [K(thf)(4)] (5), [CpTi(NPtBu3)(PPh)(3)] (7) and [CpTi(NPtBu3)(mu-PHPh)](2) (8), while reaction of 6 with (C(6)H(2)tBu3)PH2 in the presence of PMe3 afforded [CpTi(NPtBu3)(PMe3)(p(C(6)H(2)tBu(3))] (10). The secondary phosphines Ph2PH and (PhHPCH2)(2)CH2 also undergo dehydrocoupling affording (Ph2P)(2) and (PhPCH2)(2)CH2. 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*Zr-2(H)(PH)(2)C6H4] [Li(thf)(4)] (22), [Cp*Ti(NPtBu3)(PH)(2)C6H4](2) (23) and [Cp*Ti(NPtBu3)(PH)(2)C6H4] (24). Mechanistic implications are discussed.

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