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A mixed-valent cyclodiphosphazane: Transition metal chemistry and cis/trans isomerisation

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Abstract

The hydrolysis of cis-{ClP(μ-N tBu)2P(NHtBu)} (1) produced a mixed PIII/P V derivative of cyclodiphosphazane, cis-{(tBuNH)P(μ-N tBu)2P(O)H} (2). The treatment of 2 with elemental selenium resulted in the formation of the monoselenide, trans-{(tBuNH)P(Se)(μ-N tBu)2P(O)H} (3) in good yield. The reactions of two equivalent of 2 with [Pd(μ-Cl)(η 3-C3 H 5)]2 or [Ru(η 6-p-cymene)(μ-Cl)Cl]2 in dichloromethane afforded corresponding mononuclear complexes, [(η 3-C3 H 5)PdCl{(tBuNH)P(μ-N tBu)2P(O)H}] (4) and [((η 6-p-cymene)RuCl2){(tBuNH)P(μ-NtBu)2P(O)H}] (5). The treatment of 2 with M(COD)Cl2 (M = Pd and Pt) in dichloromethane at room temperature gave [MCl2{(tBuNH)P(μ-N tBu)2P(O)H}2] (6 M = Pd; 7 M = Pt) in good yield. Owing to the cis/trans isomerisation of the cyclodiphosphazane rings, the complexes 6 and 7 exist as a mixture of two isomers. Various NMR spectroscopic techniques were employed for structural elucidation. The molecular structures of 5 and 7 were established by single crystal X-ray crystallographic studies.

Transition metal complexes of a mixed-valent cyclodiphosphazane are described.

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Acknowledgements

We are grateful to the Science & Engineering Research Board, New Delhi, India. for financial support of this work through grant No.SB/S1/IC-08/2014. GSA thanks CSIR, New Delhi, for Senior Research Fellowship (SRF). We also thank the Department of Chemistry Instrumentation Facilities, IIT Bombay, for spectral and analytical data. JTM thanks the Louisiana Board of Regents for the purchase of the CCD diffractometer and the Chemistry Department of Tulane University for support of the X-ray laboratory.

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Authors and Affiliations

  1. Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400 076, India

    GUDDEKOPPA S ANANTHNAG & MARAVANJI S BALAKRISHNA

  2. Department of Chemistry, Tulane University, New Orleans, Louisiana, 70118, USA

    JOEL T MAGUE

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  1. GUDDEKOPPA S ANANTHNAG
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  2. JOEL T MAGUE
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Correspondence to MARAVANJI S BALAKRISHNA.

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Supplementary Information

NMR spectra for compounds 3–7 are provided. The electronic supplementary information can be seen at www.ias.ac.in/chemsci. Crystallographic data for compounds 5 and 7 has been deposited at the Cambridge Crystallographic Data Centre with CCDC no. 1000229 (compound 5) and 1000230 (compound 7). These data can be obtained free of charge at www.ccdc.cam.ac.ul/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: + 44(0)1223-336033; E-mail: deposit@ccdc.cam.ac.uk].

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ANANTHNAG, G.S., MAGUE, J.T. & BALAKRISHNA, M.S. A mixed-valent cyclodiphosphazane: Transition metal chemistry and cis/trans isomerisation. J Chem Sci 127, 979–986 (2015). https://doi.org/10.1007/s12039-015-0865-3

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