Molecular Recognition Using Ruthenium(II) Porphyrin Thiol Complexes as Probes
Molecular Recognition Using Ruthenium(II) Porphyrin Thiol Complexes as Probes
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DOI：
10.1021/ic302401m
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发表时间：
2013-01-21
影响因子：
4.6
通讯作者：
James, Brian R.
中科院分区：
文献类型：
--
作者：
Reboucas, Julio S.;James, Brian R.
报道了106种Ru(porp)(RSH)(2)的原位H-1 NMR数据，其中porp是β -八乙基卟啉（OEP），中四苯基卟啉（TPP）及其对取代四苯基类似物（T-p-XPP; X = OMe, Me， F, Cl, CO2Me, CF3），中四基（3,5-二甲基苯基）卟啉（T-m,m'-Me2PP）和中四苯基卟啉（TMP）， R = Me, Et, Pr-n, Pr-i, Bu-n, Bu-t, (n)Hex, Bn（苄基），Ph和p-MeOC6H4。巯基配位时SH共振的前场位移反映了卟啉环电流的变化，并使用经验模型进行了分析，该模型定量地描述了巯基配体（其中空间因子占主导地位）和卟啉平面（其中电子因子占主导地位）之间的非键、电子和空间相互作用；这种相互作用通常涉及金属卟啉系统中的小分子识别。研究结果对血红蛋白和表面配位化学的意义也作了简要介绍。
In situ H-1 NMR data are reported for 106 Ru(porp)(RSH)(2) species, where porp is the dianion of beta-octaethylporphyrin (OEP), meso-tetraphenylporphyrin (TPP), and its para-substituted tetraphenyl analogues (T-p-XPP; X = OMe, Me, F, Cl, CO2Me, CF3), meso-tetrakis(3,5-dimethylphenyl)porphyrin (T-m,m'-Me2PP), and meso-tetramesitylporphyrin (TMP), and R = Me, Et, Pr-n, Pr-i, Bu-n, Bu-t, (n)Hex, Bn (benzyl), Ph, and p-MeOC6H4. The upfield shifts in the SH resonances upon coordination of the thiol reflect changes in the porphyrin ring current and are analyzed using an empirical model that depicts quantitatively the nonbonding, electronic, and steric interactions between the thiol ligands, where steric factors dominate, and the porphyrin plane, where electronic factors dominate; such interactions are typically involved in small-molecule recognition within metalloporphyrin systems. Implications of the findings to hemethiolate proteins and surface coordination chemistry are also briefly presented.