Synthesis and characterization of osmium nitrosyl porphyrins containing organo, halogeno, and μ-Oxo ligands, and extensions to the first organometallic thionitrosyl porphyrin

Lin Cheng, Li Chen, Hee Sun Chung, Masood A. Khan, George B. Richter-Addo, Victor G Young

Research output: Contribution to journalArticle

25 Scopus citations

Abstract

The sequential reaction of (OEP)Os(CO) with NOPF6 (in CH2Cl2) followed by RMgX (in THF) gives variable isolated yields of the new (OEP)Os(NO)R (5-44%), (OEP)Os(R)2 (1-10%), (OEP)Os(NO)X (14-19%), and [(OEP)Os(NO)]2(μ-O) (up to 24%) compounds, depending on the reaction conditions and the nature of R and X (OEP = octaethylporphyrinato dianion; R = Me, Et, iPr, tBu, p-C6H4F; X = Cl, Br). The IR υNO values of the complexes (in CH2Cl2) decrease in the order (OEP)Os(NO)X (1799-1795 cm-1) > [(OEP)Os(NO)]2(μ-O) (1770 cm-1) > (OEP)Os(NO)R (1748-1703 cm-1). The δmeso peaks in the 1H NMR spectra of the (OEP)-Os complexes (in CDCl3) also decrease in the order (OEP)Os(NO)X (10.41-10.40 ppm) > [(OEP)Os(NO)]2(μ-O) (10.35 ppm) > (OEP)Os(NO)R (10.24-10.21 ppm) > (OEP)Os(R)2 (9.71-9.03 ppm). The thionitrosyl (OEP)Os(NS)Cl and (OEP)Os(NS)Me compounds have also been prepared. The solid-state molecular structures of [(OEP)Os(NO)]2(M-O), (OEP)Os(NS)Cl, and (OEP)Os(NS)Me have been determined by single-crystal X-ray diffraction.

Original languageEnglish (US)
Pages (from-to)3853-3864
Number of pages12
JournalOrganometallics
Volume17
Issue number18
DOIs
StatePublished - Aug 31 1998

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