Abstract

The reaction between the tricobalt cluster FcCCo 3(CO) 9 ( 1) (where Fc = ferrocenyl) and the redox-active diphosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma) affords the new cluster ▪ ( 3) in refluxing 1,2-dichloroethane or toluene. The cluster FcCCo 3(CO) 7(bma) ( 2), a logical precursor to 3, was observed in solution by IR spectroscopy when cluster 1 and bma were refluxed in the low boiling point solvent CH 2Cl 2; however, putative 2 could not be isolated due to its rapid conversion to the final product 3. Cluster 3 has been fully characterized in solution by IR and NMR ( 13C and 31P) spectroscopy and in the solid state by X-ray diffraction analysis. ▪, as the CH 2Cl 2 solvate, crystallized in the triclinic space group P 1, a = 10.4704(6), b = 14.6033(8), c = 14.787(1) A ̊ , α = 102.973(5), β = 94.517(8), γ = 90.197(5)°, V = 2195.9(2) A ̊ 3, Z = 2, D calc = 1.653 g cm −3; R = 0.0411, R w = 0.0449 for 3602 observed reflections with 13 σ( I). Cyclic voltammetric investigations of 3 in CH 2Cl 2 reveal the presence of three reversible redox responses assigned to the 0/1 +, 0/1 −1, and 1 −/2 − redox couples. The nature of the HOMO and the two lowest unoccupied molecular orbitals (LUMO and SUMO) in 3 has been determined by carrying out extended Hückel calculations on the model compound ▪, the results of which are discussed relative to the observed electrochemistry of 3 and related cluster compounds.

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