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Carbon monoxide and nitrogen monoxide ligand dynamics in synthetic heme and heme-copper complex systems.


ABSTRACT: Intermolecular nitrogen monoxide (*NO) and carbon monoxide (CO) transfer from iron to copper and back, a phenomenon not previously observed, has been accomplished by employing transient-absorbance laser flash photolysis methods. A 1:1 heme/copper component system consisting of a six-coordinate ferrous species, F(8)Fe(II)(CO)(DCIM) or F(8)Fe(II)(NO)(thf) [F(8) = tetrakis(2,6-difluorophenyl)porphyrinate(2-); DCIM = 1,5-dicyclohexylimidazole; thf = tetrahydrofuran], and two ligand-copper(I) complexes, one with tridentate [(Bz)L = (benzyl)bis(2-pyridylmethyl)amine] and one with tetradentate coordination [(Py)L = tris(2-pyridylmethyl)amine], was utilized. The results suggest a lower affinity for NO versus CO binding to copper(I) and a higher rate for NO versus CO binding to heme. In fact, the latter event has been observed in cytochrome c oxidase aa(3).

SUBMITTER: Lucas HR 

PROVIDER: S-EPMC2771263 | biostudies-literature | 2009 Oct

REPOSITORIES: biostudies-literature

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Carbon monoxide and nitrogen monoxide ligand dynamics in synthetic heme and heme-copper complex systems.

Lucas Heather R HR   Meyer Gerald J GJ   Karlin Kenneth D KD  

Journal of the American Chemical Society 20091001 39


Intermolecular nitrogen monoxide (*NO) and carbon monoxide (CO) transfer from iron to copper and back, a phenomenon not previously observed, has been accomplished by employing transient-absorbance laser flash photolysis methods. A 1:1 heme/copper component system consisting of a six-coordinate ferrous species, F(8)Fe(II)(CO)(DCIM) or F(8)Fe(II)(NO)(thf) [F(8) = tetrakis(2,6-difluorophenyl)porphyrinate(2-); DCIM = 1,5-dicyclohexylimidazole; thf = tetrahydrofuran], and two ligand-copper(I) complex  ...[more]

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