A Complete Family of Isostructural Cluster Compounds with Cubane-like M3S4M' Cores (M = Mo, W; M' = Ni, Pd, Pt): Comparative Crystallography and Electrochemistry
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- 作者：Konrad Herbst ; Piero Zanello ; Maddalena Corsini ; Nicola D'Amelio ; Lutz Dahlenburg ; and Michael Brorson
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：February 24, 2003
- 年：2003
- 卷：42
- 期：4
- 页码：974 - 981
- 全文大小：162K
- 年卷期：v.42,no.4(February 24, 2003)
- ISSN：1520-510X
文摘
By reaction of the geometrically incomplete cubane-like clusters [(
5-Cp')3Mo3S4)][pts] and [(5-Cp')3W3S4][pts](Cp' = methylcyclopentadienyl; pts = p-toluenesulfonate) with group 10 alkene complexes, three new heterobimetallicclusters with cubane-like cluster cores were isolated: [(5-Cp')3W3S4M'(PPh3)][pts] ([5][pts], M' = Pd; [6][pts], M'= Pt); [(5-Cp')3Mo3S4Ni(AsPh3)][pts] ([7][pts]). The compounds [5][pts]-[7][pts] are completing the extensive seriesof clusters [(5-Cp')3M3S4M'(EPh3)][pts] (M = Mo, W; M' = Ni, Pd, Pt; E = P, As) which allows the consequencesof replacing a single type of atom on structural and NMR and UV/vis spectroscopic as well as electrochemicalproperties to be determined. Single-crystal X-ray structure determinations of [5][pts]-[7][pts] revealed that [5][pts]was not isomorphous to the other members of the series [(5-Cp')3M3S4M'(EPh3)][pts] due to distinctly different cellparameters, which in the molecular structure of [5]+ is reflected in a slightly different orientation of the PPh3 ligand.Electrochemical measurements on the series showed that the Mo-based clusters were more difficult to oxidizethan their W-based analogues. The Pd-containing clusters underwent two-electron oxidation processes, whereasthe Ni- and Pt-containing clusters underwent two separated one-electron oxidation processes.
5-Cp')3Mo3S4)][pts] and [(5-Cp')3W3S4][pts](Cp' = methylcyclopentadienyl; pts = p-toluenesulfonate) with group 10 alkene complexes, three new heterobimetallicclusters with cubane-like cluster cores were isolated: [(5-Cp')3W3S4M'(PPh3)][pts] ([5][pts], M' = Pd; [6][pts], M'= Pt); [(5-Cp')3Mo3S4Ni(AsPh3)][pts] ([7][pts]). The compounds [5][pts]-[7][pts] are completing the extensive seriesof clusters [(5-Cp')3M3S4M'(EPh3)][pts] (M = Mo, W; M' = Ni, Pd, Pt; E = P, As) which allows the consequencesof replacing a single type of atom on structural and NMR and UV/vis spectroscopic as well as electrochemicalproperties to be determined. Single-crystal X-ray structure determinations of [5][pts]-[7][pts] revealed that [5][pts]was not isomorphous to the other members of the series [(5-Cp')3M3S4M'(EPh3)][pts] due to distinctly different cellparameters, which in the molecular structure of [5]+ is reflected in a slightly different orientation of the PPh3 ligand.Electrochemical measurements on the series showed that the Mo-based clusters were more difficult to oxidizethan their W-based analogues. The Pd-containing clusters underwent two-electron oxidation processes, whereasthe Ni- and Pt-containing clusters underwent two separated one-electron oxidation processes.