Abstract
The reaction between the tetrahedrane cluster PhCCo3(CO)9 (1) and the redox-active diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) leads to the replacement of two CO groups and formation of PhCCo3(CO)7(bpcd) (2). Cluster 2 is thermally unstable and readily transforms into the new cluster \({\text{Co}}_{\text{3}} ({\text{CO)}}_6 [\mu _2 {\text{ - }}\eta ^2 :\eta ^1 {\text{ - C(Ph)C}} = {\text{C(PPh}}_{\text{2}} ){\text{C(O)CH}}_{\text{2}} {\text{C(O)] - (}}\mu _{\text{2}} {\text{ - PPh}}_{\text{2}})\) (3). Both clusters 2 and 3 have been isolated and fully characterized in solution by IR and NMR (31P and 13C) spectroscopy. VT 31P NMR data indicate that the bpcd ligand in PhCCo3(CO)7(bpcd) is fluxional in solution, with two chelating and one bridging isomer being observed at 176 K in THF. The kinetics for the conversion of 2 to 3 followed first-order kinetics in 1,2-dichloroethane (DCE). These data, coupled with the reaction rates being retarded in the presence of added CO, and the activation parameters (ΔH ‡ = 27.1 ± 0.3 kcal/mol and ΔS ‡ = 9 ± 1 eu) support a scheme involving a dissociative CO loss as the rate-limiting step. Clusters 2 and 3 have been structurally characterized by X-ray diffraction analyses. PhCCo3(CO)7(bpcd) crystallizes in the monoclinic space group P21/n: a = 10.731(2) Å, b = 21.743(3) Å, c = 17.143(1) Å, β = 97.522(8)°, V = 3965.4(8) Å3, Z = 4, d calc = 1.552 g · cm−3; R = 0.0598, R w = 0.0671 for 1428 observed reflections with l > 3σ(l). \({\text{Co}}_{\text{3}} ({\text{CO)}}_6 [\mu _2 {\text{ - }}\eta ^2 :\eta ^1 {\text{ - C(Ph)C}} = {\text{C(PPh}}_{\text{2}} ){\text{C(O)CH}}_{\text{2}} {\text{C(O)] - (}}\mu _{\text{2}} {\text{ - PPh}}_{\text{2}})\) crystallizes in the triclinic space group P\(\overline {\text{1}}\) a = 11.572(1) Å, b = 11.702(1) Å, c = 15.227(1) Å, α = 106.716(6)°, β = 90.419(6)°, γ = 103.676(7)°, V = 1912.4(3) Å3, Z = 2, d calc = 1.560 g · cm−3; R = 0.0545, R w = 0.0632 for 3149 observed reflections with l > 3σ(l). The chemistry exhibited by clusters 2 and 3 is compared with related clusters containing the diphosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma).
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Bott, S.G., Shen, H. & Richmond, M.G. CO Substitution in PhCCo3(CO)9 by 4,5-Bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Ligand Fluxionality, Kinetics, and X-Ray Structures of PhCCo3(CO)7(bpcd) and \({\text{Co}}_{\text{3}} ({\text{CO)}}_6 [\mu _2 {\text{ - }}\eta ^2 ,\eta ^1 {\text{ - C(Ph)C}} = {\text{C(PPh}}_{\text{2}} ){\text{C(O)CH}}_{\text{2}} {\text{C(O)] - (}}\mu _{\text{2}} {\text{ - PPh}}_{\text{2}})\) . Structural Chemistry 12, 225–235 (2001). https://doi.org/10.1023/A:1016664024371
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DOI: https://doi.org/10.1023/A:1016664024371