• Synthesis and unexpected reactivity of [Ru(𝜂6 -cymene)Cl2 (PPh2 Cl)], leading to [Ru(𝜂6 -cymene)Cl2 (PPh2H)] and [Ru(𝜂6-cymene)Cl2 (PPh2OH)] complexes

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    • Keywords

       

      1-Phenylethane-1,2-diol; chlorodiphenylphosphine; diphenylphosphine; diphenylphosphinous acid; half sandwich ruthenium complexes.

    • Abstract

       

      The reaction of [Ru(𝜂6-cymene)Cl2]2 and PPh2Cl in the ratio 1:2 gives a stable [Ru(𝜂6-cymene) Cl2(PPh2Cl)] complex. Attempts to make the cationic [Ru(𝜂6-cymene)Cl(PPh2Cl)2]Cl with excess PPh2Cl and higher temperatures led to adventitious hydrolysis and formation of [Ru(𝜂6-cymene)Cl2 (PPh2OH)]. Attempts to make a phosphinite complex by reacting [Ru(𝜂6-cymene)Cl2]2 with PPh2Cl in the presence of an alcohol results in the reduction of PPh2Cl to give [Ru(𝜂6-cymene)Cl2(PPh2H)] and the expected phosphinite. The yield of the hydride complex is highest when the alcohol is 1-phenyl-ethane-1,2-diol. All three half-sandwich complexes are characterized by X-ray crystallography. Surprisingly, the conversion of chlorodiphenylphosphine to diphenylphosphine is mediated by 1-phenyl-ethane-1,2-diol even in the absence of the ruthenium half-sandwich precursor.

    • Author Affiliations

       

      Arun Kumar Pandiakumar1 Ashoka G Samuelson1

      1. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India
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