Abstract
A series of piano-stool complexes of the cymantrene family (cymantrene = Mn(η5-C5H5)(CO)3, 1) undergoes facile replacement of a carbonyl ligand by P(OPh)3 when oxidized by one-electron in CH2Cl2/[NBu4][B(C6F5)4]. Data on the previously characterized complexes 1, Mn(η5-C5H4NH2)(CO)3 (3) and Mn(η5-C5Me5)(CO)3 (6) have been supplemented by cyclic voltammetry (CV) and IR spectroscopy on Mn(η5-C5H4Me)(CO)3 (2), Mn(η5-C5H4I)(CO)3 (4), and Mn(η5-C5H4C(O)H)(CO)3 (5). The substitution rates, determined by digital simulations of CV scans, ranged from 4 M−1 s−1 for 6 + to 3 × 105 M−1 s−1 for 5 +. In general, a more strongly donating cyclopentadienyl substituent slows down the CO substitution rate. For mono-cyclopentadienyl substituted complexes, the logarithm of ksub is shown to increase linearly with either the weighted average of the CO stretching frequencies or the E1/2 value of the redox process. An exception to this generalization is the amine-substituted complex 3, for which the CO-substitution rate is higher than predicted by its E1/2 potential. The substitution rate of the pentamethylated Cp complex 6 + is slowed by about an order of magnitude owing to steric effects. The efficacy of this method to predict the CO-substitution rate of a cymantrene-tagged molecule was tested with a cymamtrene-derivatized diarylethene complex, 7. The measured P(OPh)3-for-CO substitution rate of 3.7 × 102 M−1 s−1 for 7 + was very close to that predicted by the E1/2 value of 7. A ligand electronic parameter, EL, of 0.62 was determined for the triphenylphosphite ligand. These studies build on the previous CO substitution-rate analyses by Sweigart and others.
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Acknowledgments
The authors are grateful for support of this work by the National Science Foundation (CHE-0808909 and CHE-1212339). One of the authors (WEG) was a postdoctoral associate at Northwestern University when Dwight Sweigart was finishing his Ph.D. studies. He shared research interests and friendship with Dwight for many years, and grew in admiration of Dwight’s contributions to organometallic chemistry and of his high scientific and ethical standards.
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The authors dedicate this paper to the memory of prof. Dwight A. Sweigart.
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Wu, K., Laws, D.R., Nafady, A. et al. Substitution of CO Ligand by P(OPh)3 in Radical Cations of the Cymantrene Family: Relationships of Substitution Rates to E1/2 Values and Carbonyl IR Frequencies. J Inorg Organomet Polym 24, 137–144 (2014). https://doi.org/10.1007/s10904-013-9976-9
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DOI: https://doi.org/10.1007/s10904-013-9976-9