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-C5
tBu3H2)][PF6]
(10a
+
) and
[Rh(η5-C5H5)(η5-C5
tBu3H2)][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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