Carbon Monoxide and Nitrogen Monoxide Ligand Dynamics in Synthetic Heme and Heme−Copper Complex Systems,Journal of the American Chemical Society

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Carbon Monoxide and Nitrogen Monoxide Ligand Dynamics in Synthetic Heme and Heme−Copper Complex Systems
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2009-10-07 , DOI: 10.1021/ja906172c
Heather R Lucas ₁ , Gerald J Meyer , Kenneth D Karlin

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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).

中文翻译：

合成血红素和血红素-铜络合物系统中的一氧化碳和一氧化氮配体动力学

分子间一氧化氮 (*NO) 和一氧化碳 (CO) 从铁转移到铜并返回，这是以前未观察到的现象，已通过采用瞬态吸收激光闪光光解方法实现。一种 1:1 血红素/铜组分系统，由六配位亚铁物质 F(8)Fe(II)(CO)(DCIM) 或 F(8)Fe(II)(NO)(thf) [F( 8) = 四(2,6-二氟苯基)卟啉(2-)；DCIM = 1,5-二环己基咪唑；thf = 四氢呋喃]，以及两种配体-铜 (I) 配合物，一种具有三齿 [(Bz)L = (苄基)双 (2-吡啶基甲基)胺]，一种具有四齿配位 [(Py)L = tris(2-吡啶基甲基）胺]，被利用。结果表明 NO 与 CO 结合铜 (I) 的亲和力较低，NO 与 CO 结合血红素的速率较高。事实上，已在细胞色素 c 氧化酶 aa(3) 中观察到后一种事件。

更新日期：2009-10-07

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