The reactions of chlorohydrido- and dichloro-tris(triphenylphosphine)ruthenium(II) with alkali hydroxides and alkoxides. Hydridohydroxobis(triphenylphosphine)ruthenium(II) monosolvates, their reactions and related compounds
Abstract
The interaction of chlorohydridotris(triphenylphosphine)ruthenium(II) with NaOH or KOH in tetrahydrofuran, acetone, or t-butyl alcohol leads, depending on conditions, first to red, five-co-ordinate complexes RuH(OH)(PPh3)2(sol)(sol = thf or H2O) secondly to hydroxo-bridged dimers, (PPh3)2H(sol)Ru(µ-OH)2Ru(sol)H(PPh3)2(sol = Me2CO, H2O, or ButOH) and thirdly to a tetranuclear complex of stoicheiometry Ru4H4(OH)2(PPh2)2(CO)2(PPh3)6(Me2CO)2.
Interaction of dichlorotris(triphenylphosphine)ruthenium(II) with KOH gives similar compounds, RuCl(OH)(PPh3)2(sol)2 and {RuCl(OH)(PPh3)2(sol)}2(sol = H2O or thf) as well as {RuH(OH)(PPh3)2(thf)}2.
The interaction of RuHCl(PPh3)3 with sodium methoxide gives rise to two compounds that are formulated, respectively as having Ru–CHO and Ru–OCH2 groups, The mechanism of decarbonylation of alcohols is discussed and the compounds RuH2(CO)(PPh3)2·ROH (R = Me or Et) are synthesised.
I.r. and 1H and 31P n.m.r. spectra of the various complexes are given and structures for the compounds proposed on this basis.
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