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Coordination of the Hemilabile Ligand Diphenylvinylphosphine to Ru4(µ-H)4(CO)12: Synthesis, Stability and Structural Studies

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Abstract

The tetraruthenium tetrahydrido carbonyl cluster Ru4(µ-H)4(CO)12 (1) reacts with diphenylvinylphosphine under thermal activation to give the substitution products Ru4(µ-H)4(CO)12−n(κ1-Ph2PCH=CH2)n, (2) (n = 3 (a); 4 (b)). Both 2a and 2b have been completely characterized, including by single-crystal X-ray diffraction analysis. Each of the diphenylvinylphosphine ligands in 2a and 2b is terminally bound, via the phosphorus atom, to a different ruthenium metal center, while the hydride positions in the Ru4(µ-H)4 cores retain the D2d symmetry of the parent cluster 1. Clusters 2a and 2b were able to retain their structural integrity at elevated temperatures.

Graphic Abstract

Thermolysis of Ru4(μ-H)4(CO)12 (1) in cyclohexane with diphenylvinylphosphine afforded the tri- and tetra-substituted derivatives Ru4(μ-H)4(CO)9(κ1-Ph2PCH=CH2)3 (2a) and Ru4(μ-H)4(CO)8(κ1-Ph2PCH=CH2)4 (2b). For both substituted clusters, the diphenylvinylphosphine ligands are bound terminally to the tetraruthenium core via the phosphorus atoms while the hydride positions retain the D2d symmetry of the parent cluster 1.

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Acknowledgments

This work was supported by Hwa Chong Institution as well as Nanyang Technological University and the Ministry of Education with a research Grant (No. M4011158).

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Authors and Affiliations

  1. Hwa Chong Institution, 661 Bukit Timah Road, Singapore, 269734, Singapore

    Ren Kai Edward Neo, Han Wee Ong & Yong Leng Kelvin Tan

  2. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore

    Zhen Xuan Wong, Elumalai Kumaran, Rakesh Ganguly & Weng Kee Leong

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  1. Ren Kai Edward Neo
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Correspondence to Weng Kee Leong or Yong Leng Kelvin Tan.

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10876_2021_2150_MOESM1_ESM.pdf

Supplementary file1 (PDF 518 kb) Supplementary Material: CCDC 1517034‒1517035 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif. IR, NMR and ESI–MS spectra for 2a and 2b.

Supplementary file 2 (CIF 784 kb)

Supplementary file 3 (CIF 745 kb)

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Neo, R.K.E., Ong, H.W., Wong, Z.X. et al. Coordination of the Hemilabile Ligand Diphenylvinylphosphine to Ru4(µ-H)4(CO)12: Synthesis, Stability and Structural Studies. J Clust Sci 33, 2337–2343 (2022). https://doi.org/10.1007/s10876-021-02150-0

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