Rhodocenium Complexes Bearing the 1,2,3-Tri- tert -butylcyclopentadienyl Ligand: Redox-Promoted Synthesis and Mechanistic, Structural and Computational Investigations
1998; American Chemical Society; Volume: 17; Issue: 9 Linguagem: Inglês
10.1021/om9707735
ISSN1520-6041
AutoresBernadette T. Donovan-Merkert, C. Reid Clontz, Leslie M. Rhinehart, Howard I. Tjiong, Clifford M. Carlin, Thomas R. Cundari, Arnold L. Rheingold, Ilia A. Guzei,
Tópico(s)Ferrocene Chemistry and Applications
ResumoSingle-electron oxidation of rhodium complexes containing the 1,2,3,5-η-penta-2,4-dienediyl ligand was conducted by electrochemical and chemical means. In all cases, rhodocenium complexes bearing the η5-1,2,3-tri-tert-butylcyclopentadienyl ligand were produced in good yield. The results of single-crystal X-ray diffraction studies revealed the solid-state structures of [Rh(η5-C5H5)(η5-C5tBu3H2)][PF6] (10a+) and [Rh(η5-C5H5)(η5-C5tBu3H2)][BF4] (10b+). The steric strain in these molecules is apparently relieved by in-plane distortions of the bond lengths and angles of the tri-tert-butylcyclopentadienyl ligand. The results of a deuterium-labeling study revealed the stereochemistry of the ring-closure reaction. Computational studies using the PM3 semiempirical Hamiltonian suggest that oxidation of the pentadienediyl complexes involves removal of an electron from a molecular orbital centered on the pentadienediyl ligand.
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