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DOI: 10.1039/A700588A (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 2113-2118

Synthesis and reactivity of [Ru{HB(pz)3}{P(C6H11) 3}Cl(OCH2R)] (pz = pyrazolyl, R = H or Me)[hair space]

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Christian Gemel, Guido Kickelbick, Roland Schmid and Karl Kirchner

Abstract

The complex [Ru{HB(pz)3}(cod)Cl] 1 (cod = cycloocta-1,5-diene) reacted with P(C6H11)3 ([greater than or equal, slant]1 equivalent) in boiling dimethylformamide (dmf) to give the highly air-sensitive intermediate [Ru{HB(pz)3}{P(C6H11) 3}Cl(dmf)] which, on exposure to air in either ethanol or methanol as the solvent, was converted to the ruthenium(III) complexes [Ru{HB(pz)3}{P(C6H11) 3}Cl(OCH2R)] (R = Me 2a or H 2b) in good yields. Complex 2b has been characterized by X-ray crystallography. Treatment of 2a or 2b with L = MeCN, pyridine, CO, P(OMe)3, or PMe3 in CH2Cl2 afforded the (diamagnetic) ruthenium(II) compounds [Ru{HB(pz)3}{P(C6H11) 3}(Cl)L] 3–7. Most remarkably, 2a or 2b reacted also with terminal alkynes HC[triple bond, length as m-dash]CR (R = Ph, CO2Et, Bun or SiMe3) giving the neutral vinylidene complexes [Ru{HB(pz)3}{P(C6H11) 3}Cl ([double bond, length as m-dash]C[double bond, length as m-dash]CHR)] 8–11. Preliminary results of a study of the catalytic activity of 2 are also presented. Thus, 2a and 2b catalysed the dimerization of some terminal alkynes HC[triple bond, length as m-dash]CR (R = Ph, CO2Et or SiMe3).

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