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Synthesis, structure and reactivity of homobimetallic Rh(I) and Ir(I) complexes of s- and as-indacene-diide |
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| Authors: | Alberto Ceccon Annalisa Bisello Laura Crociani Alessandro Gambaro Paolo Ganis Francesco Manoli Saverio Santi and Alfonso Venzo |
| Institution: | a Department of Physical Chemistry, University of Padova, via Loredan 2, I-35131 Padua, Italy b CNR, Centro di Studi sugli Stati Molecolari Radicalici ed Eccitati, via Loredan 2, I-35131 Padua, Italy |
| Abstract: | The Rh(COD) and Ir(COD) homobimetallic complexes of s-indacene-diide, 2,6-dimethyl-s-indacene-diide, as-indacene-diide, and 2,7-dimethyl-as-indacene-diide have been synthesized from the di-lithium salts of the dianions and metal dimers M(μ-Cl)L2]2 (M = Rh, Ir; L2 = COD, NBD, (ethylene)2, (CO)2 as mixtures of syn and anti isomers. The syn/anti ratio depends on the nature of the ancillary ligands at the metal and on the s or as geometry of the bridging ligand. In the reaction of the 2,7-dimethyl-as-indacene-diide-M(COD)]2 species with CO, the higher reactivity of the syn isomers has been justified on the basis of a greater instability of the ground state due to steric interactions between the COD groups. Bis-η1 metal-bonded intermediates have been identified in the carbonylation of iridium derivatives; on the other hand, the formation of the bis-η5 mixed complexes syn and anti-{2,7-dimethyl-as-indacene-diide-Rh(COD)]Rh(CO)2]} and their reactivity strongly support the existence of metal---metal interaction in the rhodium derivatives. |
| Keywords: | Indacene-diide complexes Rhodium complexes Iridium complexes Syn/anti isomers Cooperative effects |
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