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Ligand substitution reaction in the parent cluster (μ3-FcCHC)FeCo2(CO)9 and structural characterization of its CO substituted derivatives

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Title: Ligand substitution reaction in the parent cluster (μ3-FcCHC)FeCo2(CO)9 and structural characterization of its CO substituted derivatives
Authors: Li-Min Han1, Quan-Ling Suo1 szj@imut.edu.cn, Yi-Bing Wang1, Jie-Hui Ye1, Ning Zhu1, Xue-Bing Leng2, Jie Sun3
Source: Polyhedron. Apr2005, Vol. 24 Issue 6, p759-764. 6p.
Subjects: Metal clusters, Microclusters, Carbonyl compounds, Molecular structure
Abstract: The new mixed metal carbonyl clusters (μ3-FcCHC)FeCo2(CO)7dppm (F=C5H5FeC5H4, ferrocenyl; dppm=Ph2PCH2PPh2) (1), (μ3-FcCHC)FeCo2(CO)8L [L=PPh3 (2); AsPh3 (3)] and (μ-FcCCH)Co2(CO)5PPh3 (4) have been synthesized by facile substituted reactions. The crystal and molecular structures of 1, 2 and 3 have been determined by single crystal X-ray analysis; the ligand dppm replaces two equatorial carbonyls from two Co(CO)3 groups in the FeCo2 core, and the ligands PPh3 and AsPh3 replace one equatorial carbonyl from a Co(CO)3 group. The new compounds were characterized by IR, 1H, 13C, 31P (for 1, 2) NMR and MS. The electrochemical properties for 1, 2, 3 and 5 were investigated and the results show that the replacement of CO alters the electron density on the cluster core FeCo2 leading to a variety of interactions between FeCo2 and the apical FcCHC, and making the Fe of the ligand FcCHC in clusters 1, 2 and 3 turn into a redox center. [Copyright &y& Elsevier]
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Database: Engineering Source
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Abstract:The new mixed metal carbonyl clusters (μ3-FcCHC)FeCo2(CO)7dppm (F=C5H5FeC5H4, ferrocenyl; dppm=Ph2PCH2PPh2) (1), (μ3-FcCHC)FeCo2(CO)8L [L=PPh3 (2); AsPh3 (3)] and (μ-FcCCH)Co2(CO)5PPh3 (4) have been synthesized by facile substituted reactions. The crystal and molecular structures of 1, 2 and 3 have been determined by single crystal X-ray analysis; the ligand dppm replaces two equatorial carbonyls from two Co(CO)3 groups in the FeCo2 core, and the ligands PPh3 and AsPh3 replace one equatorial carbonyl from a Co(CO)3 group. The new compounds were characterized by IR, 1H, 13C, 31P (for 1, 2) NMR and MS. The electrochemical properties for 1, 2, 3 and 5 were investigated and the results show that the replacement of CO alters the electron density on the cluster core FeCo2 leading to a variety of interactions between FeCo2 and the apical FcCHC, and making the Fe of the ligand FcCHC in clusters 1, 2 and 3 turn into a redox center. [Copyright &y& Elsevier]
ISSN:02775387
DOI:10.1016/j.poly.2005.01.018