Journal of the American Chemical Society p. 7050 - 7056 (1989)
Update date:2022-08-17
Topics:
Proniewicz, Leonard M.
Bruha, Alan
Nakamoto, Kazuo
Kyuno, Eishin
Kincaid, James R.
Resonance Raman (RR) spectroscopic studies of O2 adducts of the imidazole complexes of a highly protected cobalt-porphyrin are reported.Strategic isotopic labeling studies, employing dioxygen isotopomers and selectively deuteriated imidazole analogues, are used to document and interpret the complicated spectral patterns that emerge as a result of complex vibrational coupling of ν(O-O) with internal modes of the trans-coordinated imidazole ligand.In addition, the observed spectral patterns are shown to be dependent upon temperature, imidazole concentration, and theaddition of a hydrogen-bond acceptor.These results indicate that hydrogen bonding of the ligated imidazole to other solution components does not lead to differences in the inherent frequency of ν(O-O) but does result in dramatic alterations of the observed spectral patterns as a consequence of diferences in vibrational coupling parameters.The implications of these studies for the interpretation of RR spectra of O2 adducts of cobalt-substituted hemeproteins are discused.
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