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Ligand-induced polyhedral opening in the mixed-metal cluster MeCCo2NiCp(CO)6 by 4,5-Bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): X-ray structure of Co2NiCp(CO)4[μ2,η2,η1-C(Me)C=C(PPh2)C(O)CH2C(O)](μ2-PPh2)

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The mixed-metal cluster MeCCo2NiCp(CO)6 (1) reacts with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) in refluxing CH2Cl2 to afford the disubstituted cluster MeCCo2NiCp(CO)4(bpcd) (2), which exists as a 1:1 mixture of bridging and chelating bpcd isomers. VT 31P NMR spectroscopy confirms that the two bpcd isomers do not interconvert in solution over the temperature range of 182–298 K. Thermolysis of cluster 2 leads to bpcd/cluster activation and formation of the phosphido-bridged cluster Co2NiCp(CO)4[μ2,η2,η1-C(Me)C=C(PPh2)C(O)CH2C(O)](μ2-PPh2) (3). The ligand-induced polyhedral expansion that accompanies the formation of the title cluster was established by X-ray diffraction analysis. Co2NiCp(CO)4[μ2,η2,η1-C(Me)C=C(PPh2)C(O)CH2C(O)](μ2-PPh2) crystallizes in the triclinic space group P-1, a=9.679(2), b=11.691(2), c=16.653(3) Å, α=85.849(3)°, β=85.456(4)°, γ=66.453(3)°, V=1720.3(6) A3, Z=2, D cacl=1.632 Mg/m3; R=0.0874, R w=0.1998 for 7053 observed reflections with I > 2σ(I).

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Acknowledgments

Financial support from the Robert A. Welch Foundation (Grants P-0074-WHW and B-1093-MGR) is appreciated.

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  1. Krzysztof Ejsmont

    Present address: Institute of Chemistry, University of Opole, Oleska 48, Opole, Poland

Authors and Affiliations

  1. Department of Chemistry, Texas Christian University, Fort Worth, TX, 76129, USA

    William H. Watson & Krzysztof Ejsmont

  2. Department of Chemistry, University of North Texas, Denton, TX, 76203, USA

    Jie Liu & Michael G. Richmond

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  1. William H. Watson
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Correspondence to William H. Watson.

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Watson, W.H., Ejsmont, K., Liu, J. et al. Ligand-induced polyhedral opening in the mixed-metal cluster MeCCo2NiCp(CO)6 by 4,5-Bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): X-ray structure of Co2NiCp(CO)4[μ2,η2,η1-C(Me)C=C(PPh2)C(O)CH2C(O)](μ2-PPh2). J Chem Crystallogr 36, 823–830 (2006). https://doi.org/10.1007/s10870-006-9142-0

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