Nitrosylation of Octaethylporphyrin Osmium Complexes with Alkyl Nitrites and Thionitrites: Molecular Structures of Three Osmium Porphyrin Derivatives.
(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](2) 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](2) with isoamyl thionitrite gives the (OEP)Os(NO)(S-i-C(5)H(11)) nitrosyl thiolate. The reaction of the [(OEP)Os](2)(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](2) 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.
Chen
Li
L
Department of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Norman, Oklahoma 73019.
Khan
Masood A.
MA
Richter-Addo
George B.
GB