137394-56-0Relevant academic research and scientific papers
Rhodocenium complexes bearing the 1,2,3-Tri-tert-butylcyclopentadienyl ligand: Redox-promoted synthesis and mechanistic, structural and computational investigations
Donovan-Merkert, Bernadette T.,Clontz, C. Reid,Rhinehart, Leslie M.,Tjiong, Howard I.,Carlin, Clifford M.,Cundari, Thomas R.,Rheingold, Arnold L.,Guzei, Ilia
, p. 1716 - 1724 (1998)
Single-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-C 5tBu3H2)][PF6] (1Oa+) and [Rh(η5C5H5)(η5-C 5tBu3H2)[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 deuteriumlabeling 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.
