Reactions of a heme-superoxo complex toward a cuprous chelate and •NO(g): CcO and NOD chemistry.
Reactions of a heme-superoxo complex toward a cuprous chelate and •NO(g): CcO and NOD chemistry.
复制标题
血红素-超氧复合物与亚铜螯合物和 αNO(g) 的反应：CcO 和 NOD 化学。
DOI：
10.1142/s108842461550025x
复制
发表时间：
2015
影响因子：
1.5
通讯作者：
Karlin,KennethD
中科院分区：
文献类型：
--
作者：
Sharma,SavitaK;Rogler,PatrickJ;Karlin,KennethD
Following up on the characterization of a new (heme)FeIII-superoxide species formed from the cryogenic oxygenation of a ferrous-heme (PPy)FeII(1) (PPy= a tetraarylporphyrinate with a covalently tethered pyridine group as a potential axial base), giving (PPy)FeIII-O2•-(2) (Li Yet al.,Polyhedron2013;58: 60–64), we report here on (i) its use in forming a cytochrome c oxidase (CcO) model compound, or (ii) in a reaction with nitrogen monoxide (•NO; nitric oxide) to mimic nitric oxide dioxygenase (NOD) chemistry. Reaction of (2) with the cuprous chelate [CuI(AN)][B(C6F5)4] (AN = bis[3-(dimethylamino)propyl]amine) gives ameta-stable product $[({\rm P}^{{\rm Py}}){\rm Fe}^{{\rm III}}-({\rm O}_{2}^{2-})-{\rm Cu}^{{\rm II}}({\rm AN})][{\rm B}({\rm C}_{6}{\rm F}_{5})_{4}]$ (3a), possessing a high-spin iron(III) and Cu(II) side-on bridged peroxo moiety with a μ-η2:η2-binding motif. This complex thermally decays to a corresponding μ-oxo complex [(PPy)FeIII-(O2-)-CuII(AN)][B(C6F5)4] (3). Both (3) and (3a) have been characterized by UV-vis,2H NMR and EPR spectroscopies. When (2) is exposed to •NO(g), a ferric heme nitrato compound forms; if 2,4-di-tert-butylphenol is added prior to •NO(g)exposure, phenolortho-nitration occurs with the iron product being the ferric hydroxide complex (PPy)FeIII(OH) (5). The latter reactions mimic the action of NOD's.
