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Backbone Modified Small Bite-Angle Diphosphines: Synthesis, Structure, Fluxionality and Regioselective Thermally-Induced Transformations of Ru3(CO)10{µ-Ph2PCH(Me)PPh2}

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Abstract

The synthesis of Ru3(CO)10{µ-Ph2PCH(Me)PPh2} (1) has been achieved from the radical-catalysed reaction of Ru3(CO)12 with 1,1′-bis(diphenylphosphino)ethane and the fluxionality, protonation and regioselective thermally-induced on-metal transformations of the small bite-angle diphosphine have been studied. Cluster 1 is fluxional in solution and variable temperature 13C{1H} NMR spectroscopy shows that the six carbonyls on the phosphine-bound metal centers interconvert rapidly on the NMR timescale. Protonation of 1 is facile at room temperature and affords the cationic-hydride [Ru3(CO)10{µ-Ph2PCH(Me)PPh2}(μ-H)][BF4] (1H +) which is fluxional, the hydride migrating between bridged and non-bridged ruthenium–ruthenium vectors, location across an unbridged metal–metal bond being thermodynamically favoured. Thermolysis of 1 in heptane affords moderate amounts of the expected benzene-CO elimination product, Ru3(CO)8(µ-CO){µ3-PhPCH(Me)PPh(C6H4)} (2), along with smaller amounts of Ru3(CO)10{μ-PhP(CHMe)(C6H4)PPh} (3) containing a novel doubly-bridged diphosphine ligand. Hydrogenation of 1 in refluxing cyclohexane affords the hydride cluster Ru3(CO)9{μ3-PhPCH(Me)PPh2}(μ-H) (4), the same species also being obtained when 2 was treated with hydrogen under similar conditions. All thermally-induced transformations are regioselective, with only a single isomer being generated. In light of the observed regioselectivity a mechanism is proposed for the formation of 2 from 1 which results from an intermediate in which the methyl-group is held over the triruthenium framework.

Graphical Abstract

Cluster Ru3(CO)10{µ-Ph2PCH(Me)PPh2} has been synthesized from the radical-catalysed reaction between Ru3(CO)12 and 1,1′-bis(diphenylphosphino)ethane and the fluxionality, protonation and regioselective thermally-induced on-metal transformations of the small bite-angle diphosphine have been investigated.

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Acknowledgments

This research was part sponsored by the Ministry of Education, Government of the People’s Republic of Bangladesh and we thank the Commonwealth Scholarship Commission for the award of a Commonwealth Scholarship (to SG).

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Authors and Affiliations

  1. Department of Chemistry, Jahangirnagar University, Dhaka-1342, Savar, Bangladesh

    Subas Rajbangshi, Shishir Ghosh & Shariff E. Kabir

  2. Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK

    Shishir Ghosh & Graeme Hogarth

  3. Department of Chemistry, King’s College London, Britannia House, 7 Trinity Street, London, SE1 1DB, UK

    Graeme Hogarth

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  1. Subas Rajbangshi
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  2. Shishir Ghosh
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  3. Graeme Hogarth
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  4. Shariff E. Kabir
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Correspondence to Graeme Hogarth or Shariff E. Kabir.

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Rajbangshi, S., Ghosh, S., Hogarth, G. et al. Backbone Modified Small Bite-Angle Diphosphines: Synthesis, Structure, Fluxionality and Regioselective Thermally-Induced Transformations of Ru3(CO)10{µ-Ph2PCH(Me)PPh2}. J Clust Sci 26, 169–185 (2015). https://doi.org/10.1007/s10876-014-0753-x

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