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Site-selective ligand substitution in CoRu(CO)7(μ-PPh2) using (Z)-Ph2PCH=CHPPh2 and reactivity of DMAD with CoRu(CO)5[(Z)-Ph2PCH=CHPPh2](μ-PPh2). X-ray structures of CoRu(CO)5[(Z)-Ph2PCH=CHPPh2](μ-PPh2) and CoRu(CO)3(μ-CO)[(Z)-Ph2PCH=CHPPh2] [μ, η3-Ph2PC(CO2Me)C(CO2Me)]

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Abstract

The heterometallic complex CoRu(CO)7(μ-PPh2) (1) reacts with the diphosphine ligand (Z)-Ph2PCH=CHPPh2 under both thermolysis and Me3NO activation to furnish CoRu(CO)5[(Z)-Ph2PCH=CHPPh2](μ-PPh2) (2) in good yield. Treatment of 2 with dimethyl acetylenedicarboxylate (DMAD) at elevated temperature leads to the formal insertion of the DMAD ligand into the Co–phosphido bond and formation of the metallocyclic compound CoRu(CO)3(μ-CO)[(Z)-Ph2PCH=CHPPh2][μ,η3-Ph2PC(CO2Me)C(CO2Me)] (3) that contains a 5e− alkenylphosphine moiety. These new CoRu compounds have been isolated by chromatography and fully characterized in solution by IR and NMR (1H and 31P) spectroscopies, and the solid-state structures of both 2 and 3 have been determined by X-ray diffraction analysis. CoRu(CO)5[(Z)-Ph2PCH=CHPPh2](μ-PPh2) crystallizes in the monoclinic space group P2 1/n, a = 11.493(8), b = 20.24(1), c = 17.04(1) Å, β = 91.03(1)°, V = 3964(5) Å3, Z = 4, D calc = 1.477 Mg/m3; R = 0.0475, R w = 0.1054 for 5120 observed reflections with I > 2σ (I). CoRu(CO)3(μ-CO)(Z)-Ph2PCH=CHPPh2][μ,η3-Ph2PC(CO2Me)C(CO2Me)], as the CH2Cl2 solvate, crystallizes in monoclinic space group P2 1/c, a = 17.0307(9) Å, b = 11.2124(6) Å, c = 24.083(1) Å, β = 97.755(1)°, V = 4556.8(4) Å3, Z = 4, D calc = 1.579 Mg/m3; R = 0.0379, R w = 0.0609 for 10774 observed reflections with I > 2σ(I). The regioselective coordination of the (Z)-Ph2PCH=CHPPh2 ligand to the two equatorial sites of the ruthenium center in 2 and the presence of the metallocyclic alkenylphosphine ligand in 3 are confirmed by the structural studies. The regiochemistry found in the coordination of (Z)-Ph2PCH=CHPPh2 to 1 is contrasted with the related diphosphine ligands bma and bpcd, while the DMAD insertion reactivity with 2 is discussed relative to alkyne reactions reported for the parent compound CoRu(CO)7(μ-PPh2).

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Authors and Affiliations

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

    William H. Watson & Krzysztof Ejsmont

  2. Department of Chemistry, University of North Texas, Denton, Texas, 76209

    Jie Liu & Michael G. Richmond

Authors
  1. William H. Watson
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  2. Krzysztof Ejsmont
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  3. Jie Liu
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  4. Michael G. Richmond
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Correspondence to Michael G. Richmond.

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Watson, W.H., Ejsmont, K., Liu, J. et al. Site-selective ligand substitution in CoRu(CO)7(μ-PPh2) using (Z)-Ph2PCH=CHPPh2 and reactivity of DMAD with CoRu(CO)5[(Z)-Ph2PCH=CHPPh2](μ-PPh2). X-ray structures of CoRu(CO)5[(Z)-Ph2PCH=CHPPh2](μ-PPh2) and CoRu(CO)3(μ-CO)[(Z)-Ph2PCH=CHPPh2] [μ, η3-Ph2PC(CO2Me)C(CO2Me)]. Journal of Chemical Crystallography 33, 775–785 (2003). https://doi.org/10.1023/A:1026159424303

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