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Ligand-mediated metal-metal interactions in (ν:ν-fulvalene) bis (dicarbonylcobalt) and rhodium complexes |
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| Authors: | Dennis L. Lichtenberger Nadine E. Gruhn Margaret E. Rempe William E. Geiger Teen T. Chin |
| Affiliation: | a Laboratory for Electron Spectroscopy and Surface Analysis, Department of Chemistry, University of Arizona, Tucson, AZ 85721, USA b Department of Chemistry, University of Vermont, Burlington, VT 05405, USA |
| Abstract: | Gas phase photoelectron spectroscopy (PES) is used to investigate the bonding and electronic structure in (fv) [M(CO)2]2 (fv = fulvalene, η5:η5-C10H82−; M = Co, Rh). The results for these bimetallic complexes are also compared to those for the analogous monometallic complexes CpM(CO)2 (Cp = η5−C5H5−; M = Co, Rh) which have been reported previously. The low valence ionization patterns observed for CpCo(CO)2 and (fv)[Co(CO)2]2 are very similar, indicating that there is little electronic interaction between the two metals of the dicobalt complex. The spectrum of (fv)[Rh(CO)2]2 also is very similar to the spectrum of CpRh(CO)2, except that the first metal ionizations in the bimetallic rhodium compound show a significant splitting (0.45 eV). This splitting is due to electronic interaction between the two metal centers which occurs via communication through the fulvalene π system. The differences in electronic structure are compared to the differences in electrochemical behavior of the Co and Rh fulvalene complexes. |
| Keywords: | Gas phase photoelectron spectroscopy Fulvalene complexes Bimetallic complexes Rhodium complexes Cobalt complexes |
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