八乙基卟啉锇配合物与亚硝酸烷基酯和硫代亚硝酸盐的亚硝基化反应：三种锇卟啉衍生物的分子结构

Nitrosylation of Octaethylporphyrin Osmium Complexes with Alkyl Nitrites and Thionitrites: Molecular Structures of Three Osmium Porphyrin Derivatives.

作者信息

Chen Li, Khan Masood A., Richter-Addo George B.

机构信息

Department of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Norman, Oklahoma 73019.

出版信息

Inorg Chem. 1998 Feb 9;37(3):533-540. doi: 10.1021/ic9708576.

DOI:10.1021/ic9708576

PMID:11670305

Abstract

(OEP)Os(CO) reacts with n-butyl nitrite to give, after workup, the (OEP)Os(NO)(O-n-Bu) trans addition product (OEP = octaethylporphyrinato dianion). Similarly, the reaction of (OEP)Os(CO) or (OEP)Os with isoamyl nitrite gives the corresponding nitrosyl alkoxide, (OEP)Os(NO)(O-i-C(5)H(11)). The related reactions of (OEP)Os(CO) or (OEP)Os with isoamyl thionitrite gives the (OEP)Os(NO)(S-i-C(5)H(11)) nitrosyl thiolate. The reaction of the (OEP)Os(PF(6))(2) reagent with isoamyl thionitrite gives the nitrosylation product, [(OEP)Os(NO)]PF(6), which undergoes anion hydrolysis to give the isolable difluorophosphate (OEP)Os(NO)(O(2)PF(2)) derivative. Interestingly, the reaction of O(2)NC(6)H(4)N=NSPh with (OEP)Os gives the (OEP)Os(SPh)(2) product with loss of the arylazo fragments. The solid-state structures of (OEP)Os(NO)(O-n-Bu), (OEP)Os(NO)(O(2)PF(2)), and (OEP)Os(SPh)(2) have been determined by X-ray crystallography.

摘要

（OEP）Os（CO）与亚硝酸正丁酯反应，后处理后得到（OEP）Os（NO）（O-n-Bu）反式加成产物（OEP = 八乙基卟啉二价阴离子）。类似地，（OEP）Os（CO）或[（OEP）Os]₂与亚硝酸异戊酯反应得到相应的亚硝酰醇盐（OEP）Os（NO）（O-i-C₅H₁₁）。（OEP）Os（CO）或[（OEP）Os]₂与亚硝酸异戊硫酯的相关反应得到亚硝酰硫醇盐（OEP）Os（NO）（S-i-C₅H₁₁）。[（OEP）Os]₂（PF₆）₂试剂与亚硝酸异戊硫酯反应得到亚硝化产物[（OEP）Os（NO）]PF₆，其经阴离子水解得到可分离的二氟磷酸盐（OEP）Os（NO）（O₂PF₂）衍生物。有趣的是，O₂NC₆H₄N=N-SPh与[（OEP）Os]₂反应得到（OEP）Os（SPh）₂产物，同时失去芳基偶氮片段。（OEP）Os（NO）（O-n-Bu）、（OEP）Os（NO）（O₂PF₂）和（OEP）Os（SPh）₂的固态结构已通过X射线晶体学确定。