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The diagnostic vibrational signature of pentacoordination in heme carbonyls.


ABSTRACT: Heme-carbonyl complexes are widely exploited for the insight they provide into the structural basis of function in heme-based proteins, by revealing the nature of their bonded and nonbonded interactions with the protein. This report presents two novel results which clearly establish a FeCO vibrational signature for crystallographically verified pentacoordination. First, anisotropy in the NRVS density of states for ?(Fe-C) and ?(FeCO) in oriented single crystals of [Fe(OEP)(CO)] clearly reveals that the Fe-C stretch occurs at higher frequency than the FeCO bend and considerably higher than any previously reported heme carbonyl. Second, DFT calculations on a series of heme carbonyls reveal that the frequency crossover occurs near the weak trans O atom donor, furan. As ?(Fe-C) occurs at lower frequencies than ?(FeCO) in all heme protein carbonyls reported to date, the results reported herein suggest that they are all hexacoordinate.

SUBMITTER: Linder DP 

PROVIDER: S-EPMC4120987 | biostudies-literature | 2014 Jul

REPOSITORIES: biostudies-literature

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The diagnostic vibrational signature of pentacoordination in heme carbonyls.

Linder Douglas P DP   Silvernail Nathan J NJ   Barabanschikov Alexander A   Zhao Jiyong J   Alp E Ercan EE   Sturhahn Wolfgang W   Sage J Timothy JT   Scheidt W Robert WR   Rodgers Kenton R KR  

Journal of the American Chemical Society 20140707 28


Heme-carbonyl complexes are widely exploited for the insight they provide into the structural basis of function in heme-based proteins, by revealing the nature of their bonded and nonbonded interactions with the protein. This report presents two novel results which clearly establish a FeCO vibrational signature for crystallographically verified pentacoordination. First, anisotropy in the NRVS density of states for ν(Fe-C) and δ(FeCO) in oriented single crystals of [Fe(OEP)(CO)] clearly reveals t  ...[more]

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