Hydridonitrosyltris triphenylphosphine ruthenium I

Submitted by J. S. BRADLEY and G. WILKINSON Checked by S. KOMIYAt and A. YAMAMOTOt 

A solution of commercial ruthenium trichloride trihydrate (1.0 g, 3.8 mmol) in water (30 mL) is placed in a 100-mL two-necked flask fitted with a reflux condenser and a gas inlet. The mixture is heated to reflux, and through the dark-brown solution is bubbled a mixture of nitric oxide and nitrogen dioxide. (This mixture may be adequately obtained by periodically introducing air into the nitric oxide stream—exact proportions of nitric oxide and nitrogen dioxide are not required). After ca. 1 hr, during which 

Hydridonitrosyltris(triphenylphosphine)ruthenium(I) is stable in air in the solid state, but slowly oxidizes in solution. The infrared spectrum of the complex shows absorptions at 1965 cm-1 [v(Ru—H)] and 1640 cm-1 [v(N—O)]. The H nmr spectrum (which is temperature-independent) shows a high-field quartet at t16.6 (2Jph = 30 Hz), consistent with a trigonal bipyramidal structure with axial hydride and equatorial phosphines.1 This structure has been confirmed in the solid state by x-ray crystallography,3 which reveals a slightly distorted trigonal bipyramid. The axial nitrosyl is coordinated in a linear fashion (Ru—N—O angle = 176°). 

Komiya, A. Yamamoto, and S. Ikeda, J. Organometal. Chem., 42, C65 (1972). [Added in proof For correct formulations see D. J. Cole-Hamilton and G. Wilkinson, Nouveau J. Chem., 1, 141 (1977)] 

HYDRIDO[ii6-PHENYL)DIPHENYLPHOSPHINE]-BIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II) TETRAFLUOROBORATE(l -) 

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