Chen Li, Khan Masood A., Richter-Addo George B.
Department of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Norman, Oklahoma 73019.
Inorg Chem. 1998 Feb 9;37(3):533-540. doi: 10.1021/ic9708576.
(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.
（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。
