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

• DOI: 10.1016/j.poly.2005.01.018
• Publication Date: 2005-04-04T09:29:06Z
• Authors: Li-Min Han; Quan-Ling Suo; Yi-Bing Wang; Jie-Hui Ye; Ning Zhu; Xue-Bing Leng; Jie Sun
• Keywords: Substitution (logic); Characterization; Substitution reaction

Abstract The new mixed metal carbonyl clusters (μ3-FcCHC)FeCo2(CO)7dppm (Fc = C5H5FeC5H4, ferrocenyl; dppm = Ph2PCH2PPh2) (1), (μ3-FcCHC)FeCo2(CO)8L [L = PPh3 (2); AsPh3 (3)] and (μ-FcC CH)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.