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

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](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.

The 3,5-dimethyl-4-nitropyrazole ligand in the construction of supramolecular networks of silver(I) complexes

“…PO 2 F 2 À occurs through a hydrolysis process which has already been observed in some examples described in the literature [14,18]. The fourth pyrazole ligand was proved to be non-coordinated, acting as a crystallisation molecule.…”

Silver and gold luminescent metallomesogens based on pyrazole ligands

“…The counteranion was generated through a hydrolysis process of the PF 6 anion during the crystallization of the starting [Ag(Hpz R(4) ) 2 ][PF 6 ] (23) (Scheme 1), this feature being frequently observed in some examples described in the literature. [30][31][32] The molecular structure of [Ag(Hpz R(4) ) 2 ][PO 2 F 2 ] (32) was determined by single X-ray diffraction methods (Fig. 3).…”

Fiber-optic infrared reflectance spectroelectrochemical studies of osmium and ruthenium nitrosyl porphyrins containing alkoxide and thiolate ligands

“…This relatively small shift of t NO (Dt NO = −50 cm −1 ) suggests a porphyrin-centered reduction process. Thus, the IR data suggests that the (OEP)Os(NO)(SEt) undergoes a fast electron transfer centered on the porphyrin (eqn (10)) followed by a structural change that involves loss of the NO from the metal center (eqn (11)).…”

“…[(OEP)Os(NO)(SEt)] − → [(OEP)Os(SEt)] − + NO (11) The IR difference spectrum which reveals the consumption of the (OEP)Ru(NO)(SEt) complex upon oxidation is shown in Fig. 10a.…”