Full title: Synthesis, characterization and electronic structure of the novel 'stellated' octahedral cluster [Co6(μ3-S)7(μ3-H)(PEt 3)6]+. Crystal and molecular structure of [Co6(μ3-S)7-(μ3-H)(PEt 3)6]0.7[Co6(μ3-S) 8(PEt3)6]0.3[BPh4]. Reaction of Co(O2CMe)2·4H2O with an excess of PEt3 and H2S afforded the novel diamagnetic octahedral cluster [Co6(μ3-S)7(μ3-H)(PEt 3)6]+ together with a minor amount of the known paramagnetic isostructural [Co6(μ3-S)8(PEt3) 6]+. Solid solutions of the two cluster cations have been isolated as the BPh4- salt. The deuteriated derivative [Co6(μ3-S)7(μ3-D)(PEt 3)6]+ has been prepared for comparison. The compounds have been characterized by 1H, 31P NMR, mass spectrometry and electrochemical measurements. The molecular structure of a sample of composition [Co6(μ3-S)7(μ3-H)(PEt 3)6]0.7[Co6(μ3-S) 8(PEt3)6]0.3[BPh4] has been determined by single-crystal X-ray diffraction. It consists of a solid solution of [Co6(μ3-S)7(μ3-H)(PEt 3)6]+ and [Co6(μ3-S)8(PEt3) 6]+. The cation [Co6(μ3-S)7(μ3-H)(PEt 3)6]0.7[Co6(μ3-S) 8(PEt3)6]0.3+ is isostructural with the series [M6(μ3-S)8(PEt3) 6]n+, having a metal-metal separation averaging 2.739(8) Å. The electronic structure of the novel hydridoderivative has been investigated through density functional calculations.
Cecconi, F., Ghilardi, C.A., Midollini, S., Orlandini, A., Zanello, P., Cinquantini, A., et al. (1995). Synthesis, Characterization and Electron Structure of the Novel 'Stellated' Octahedral Cluster [Co6(m3-S)7(m3-H)(PEt3)6]+. Crystal and Molecular Structure of [Co6(m3-S)7(m3-H)(PEt3)6]0.7[Co6(m3-S)8(PEt3)6]0.3[BPh4]. JOURNAL OF THE CHEMICAL SOCIETY DALTON TRANSACTIONS(23), 3881-3889 [10.1039/DT9950003881].
Synthesis, Characterization and Electron Structure of the Novel 'Stellated' Octahedral Cluster [Co6(m3-S)7(m3-H)(PEt3)6]+. Crystal and Molecular Structure of [Co6(m3-S)7(m3-H)(PEt3)6]0.7[Co6(m3-S)8(PEt3)6]0.3[BPh4]
Zanello P.;Cinquantini A.;Giorgi G.
1995-01-01
Abstract
Full title: Synthesis, characterization and electronic structure of the novel 'stellated' octahedral cluster [Co6(μ3-S)7(μ3-H)(PEt 3)6]+. Crystal and molecular structure of [Co6(μ3-S)7-(μ3-H)(PEt 3)6]0.7[Co6(μ3-S) 8(PEt3)6]0.3[BPh4]. Reaction of Co(O2CMe)2·4H2O with an excess of PEt3 and H2S afforded the novel diamagnetic octahedral cluster [Co6(μ3-S)7(μ3-H)(PEt 3)6]+ together with a minor amount of the known paramagnetic isostructural [Co6(μ3-S)8(PEt3) 6]+. Solid solutions of the two cluster cations have been isolated as the BPh4- salt. The deuteriated derivative [Co6(μ3-S)7(μ3-D)(PEt 3)6]+ has been prepared for comparison. The compounds have been characterized by 1H, 31P NMR, mass spectrometry and electrochemical measurements. The molecular structure of a sample of composition [Co6(μ3-S)7(μ3-H)(PEt 3)6]0.7[Co6(μ3-S) 8(PEt3)6]0.3[BPh4] has been determined by single-crystal X-ray diffraction. It consists of a solid solution of [Co6(μ3-S)7(μ3-H)(PEt 3)6]+ and [Co6(μ3-S)8(PEt3) 6]+. The cation [Co6(μ3-S)7(μ3-H)(PEt 3)6]0.7[Co6(μ3-S) 8(PEt3)6]0.3+ is isostructural with the series [M6(μ3-S)8(PEt3) 6]n+, having a metal-metal separation averaging 2.739(8) Å. The electronic structure of the novel hydridoderivative has been investigated through density functional calculations.
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https://hdl.handle.net/11365/32924
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