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Synthesis and unexpected reactivity of [Ru(η 6-cymene)Cl2(PPh2Cl)], leading to [Ru(η 6-cymene)Cl2(PPh2H)] and [Ru(η 6-cymene)Cl 2 (PPh2OH)] complexes

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Abstract

The reaction of [Ru(η 6-cymene)Cl2]2 and PPh2Cl in the ratio 1:2 gives a stable [Ru(η 6-cymene) Cl2(PPh2Cl)] complex. Attempts to make the cationic [Ru(η 6-cymene)Cl(PPh2Cl)2]Cl with excess PPh2Cl and higher temperatures led to adventitious hydrolysis and formation of [Ru(η 6-cymene)Cl2(PPh2OH)]. Attempts to make a phosphinite complex by reacting [Ru(η 6-cymene)Cl2]2 with PPh2Cl in the presence of an alcohol results in the reduction of PPh2Cl to give [Ru(η 6-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.

Synthesis and unusual reactivity of some ruthenium half-sandwich complexes including an unusual organocatalysed conversion of PPh2Cl to PPh2H are reported.

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Acknowledgements

Financial support from the Department of Science and Technology, New Delhi vide Project number, SR/S5/MBD-02/2007, is gratefully acknowledged. AKP acknowledges CSIR, New Delhi for a SRF Fellowship.

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Authors and Affiliations

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

    ARUN KUMAR PANDIAKUMAR & ASHOKA G SAMUELSON

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  1. ARUN KUMAR PANDIAKUMAR
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  2. ASHOKA G SAMUELSON
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Corresponding author

Correspondence to ASHOKA G SAMUELSON.

Additional information

Supplementary Information

CCDC 884833, 884834 and 880813 contain the supplementary crystallographic data for [Ru(η 6-cymene) Cl2(PPh2Cl)] 2 [Ru(η 6-cymene)Cl2(PPh2OH)] 4 and [Ru(η 6-cymene)Cl2(PPh2H)] 5, respectively. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. NMR spectra of complexes (figures S1-S15) are available at www.ias.ac.in/chemsci.

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PANDIAKUMAR, A.K., SAMUELSON, A.G. Synthesis and unexpected reactivity of [Ru(η 6-cymene)Cl2(PPh2Cl)], leading to [Ru(η 6-cymene)Cl2(PPh2H)] and [Ru(η 6-cymene)Cl 2 (PPh2OH)] complexes. J Chem Sci 127, 1329–1338 (2015). https://doi.org/10.1007/s12039-015-0905-z

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