Heme/non-heme diiron(II) complexes and O2, CO, and NO adducts as reduced and substrate-bound models for the active site of bacterial nitric oxide reductase
Heme/non-heme diiron(II) complexes and O2, CO, and NO adducts as reduced and substrate-bound models for the active site of bacterial nitric oxide reductase
复制标题
DOI：
10.1021/ja0458773
复制
发表时间：
2005-03-16
影响因子：
15
通讯作者：
Karlin, KD
中科院分区：
文献类型：
--
作者：
Wasser, IM;Huang, HW;Karlin, KD
作为细菌一氧化氮还原酶的反应性还原活性位点形式的第一代模型，血红素/非血红素二铁（II）络合物[（L-6）Fe-II中心点中心点Fe-II-（Cl）]（+）（2）{其中L-6 =具有栓系四齿TMPA螯合物的部分氟化四苯基卟啉; TMPA =三（2-吡啶基）胺}通过还原相应的μ-氧代二铁化合物[（L-6）Fe-III-O-Fe-III-Cl]（+）（1）生成。还原NOR与O-2，CO和NO反应的配位化学模型也被开发。与O-2和CO形成加合物，[（L-6）Fe-III（O-2（-））（thf）中心点中心点Fe-II-Cl]B（C6 F5）（4）（2a中心点O-2）{λ（max）418（Soret），536 nm; nu（O-O）= 1176 cm（-1），nu（Fe-O）= 574 cm（-1）和[（L-6）Fe-II（CO）（thf）Fe-II-Cl]B（C6F5）（4）（2a中心点CO）{nu（CO）1969 cm（-1）}。纯化的一氧化氮与2的反应导致二亚硝酰基络合物[（L-6）Fe（NO）Fe（NO）-Cl]B（C6 F5）（4）（2a中心点（NO）（2）），在1798 cm（-1）（非血红素Fe-NO）和1689 cm（-1）（血红素NO）处具有nu（NO）吸收。
As a first generation model for the reactive reduced active-site form of bacterial nitric oxide reductase, a heme/non-heme diiron(II) complex [(L-6)Fe-II center dot center dot center dot Fe-II-(Cl)](+) (2) {where L-6 = partially fluorinated tetraphenylporphyrin with a tethered tetradentate TMPA chelate; TMPA = tris(2-pyridyl)amine} was generated by reduction of the corresponding mu-oxo diferric compound [(L-6)Fe-III-O-Fe-III-Cl](+) (1). Coordination chemistry models for reactions of reduced NOR with O-2, CO, and NO were also developed. With O-2 and CO, adducts are formed, [(L-6)Fe-III(O-2(-))(thf)center dot center dot center dot Fe-II-Cl]B(C6F5)(4) (2a center dot O-2) {lambda(max) 418 (Soret), 536 nm; nu(O-O) = 1176 cm(-1), nu(Fe-O) = 574 cm(-1) and [(L-6)Fe-II(CO)(thf)Fe-II-Cl]B(C6F5)(4) (2a center dot CO) {nu(CO) 1969 cm(-1)}, respectively. Reaction of purified nitric oxide with 2 leads to the dinitrosyl complex [(L-6)Fe(NO)Fe(NO)-Cl]B(C6F5)(4) (2a center dot(NO)(2)) with nu(NO) absorptions at 1798 cm(-1) (non-heme Fe-NO) and 1689 cm(-1) (heme-NO).