Synthesis, characterization, solid-state molecular structures, and deprotonation reactions of cationic alcohol complexes of osmium nitrosyl porphyrins
Synthesis, characterization, solid-state molecular structures, and deprotonation reactions of cationic alcohol complexes of osmium nitrosyl porphyrins
复制标题
DOI：
10.1021/ic0007512
复制
发表时间：
2001-01-01
影响因子：
4.6
通讯作者：
Richter-Addo, GB
中科院分区：
文献类型：
--
作者：
Cheng, L;Powell, DR;Richter-Addo, GB
新醇盐（OEP）Os（NO）（OR）（OEP = 2，3，7，8，12，13，17，18-八乙基卟啉阴离子; R =乙基、异丙基、己基、环己基）化合物和醇[（OEP）Os（NO）（HOR）]（+）络合物（R =甲基、乙基、异丙基、己基、环己基）已经以高产率制备，并且已经通过IR、H-1 NMR和UV-vis光谱进行了充分表征，和元素分析。（OEP）Os（NO）（OEt）化合物通过单晶X射线晶体学表征。阳离子水和醇[（OEP）Os（NO）（HOR）lf配合物（R =乙基、异丙基、己基）]配合物也用单晶X射线晶体学表征，后者代表第一个锇醇结构被报道。[（OEP）Os（NO）（HOR）]（+）配合物中的亲电阳离子[（OEP）Os（NO）]（+）使配位的醇配体易于被吡啶去质子化，生成相应的醇盐（OEP）Os（NO）（OR）衍生物。提出了一种由（OEP）Os（NO）（OEt）制备新的（OEP）Os（NO）（OR）配合物的“一锅法”反应序列，该反应基于（i）乙醇化合物的初始质子化得到[（OEP）Os（NO）（HOEt）]（+）。(ii)用ROH取代醇，得到[（oEP）Os（NO）（HoR）]（+），和（iii）用吡啶将后者去质子化，得到（OEP）Os（NO）（OR）。
New alkoxide (OEP)Os(NO)(OR) (OEP = 2,3,7,8,12,13,17,1 8-octaethylporphyrinato dianion; R = ethyl, isopropyl, hexyl, cyclohexyl) compounds and alcohol [(OEP)Os(NO)(HOR)](+) complexes (R = methyl, ethyl, isopropyl, hexyl, cyclohexyl) have been prepared in high yields and have been fully characterized by IR,H-1 NMR, and UV-vis spectroscopy, and by elemental analyses. The (OEP)Os(NO)(OEt) compound was characterized by single-crystal X-ray crystallography. The cationic aqua and alcohol [(OEP)Os(NO)(HOR)lf complexes (R = ethyl, isopropyl, hexyl) complexes were also characterized by single-crystal X-ray crystallography, and the latter represent the first osmium alcohol structures to be reported. The electrophilic [(OEP)Os(NO)](+) cation in the [(OEP)Os(NO)(HOR)](+) complexes renders the coordinated alcohol ligands susceptible to deprotonation by pyridine to produce the corresponding alkoxide (OEP)Os(NO)(OR) derivatives. A one-pot reaction sequence for the preparation of new (OEP)Os(NO)(OR) complexes from (OEP)Os(NO)(OEt) was developed, which was based on (i) initial protonation of the ethoxide compound to give [(OEP)Os(NO)(HOEt)](+). (ii) alcohol substitution by ROH to give [(oEP)Os(No)(HoR)](+), and (iii) deprotonation of the latter by pyridine to give (OEP)Os(NO)(OR).