A high yield synthetic route to osmium mononitrosyls of type [OsX(NO)Q2] (2) IX = C1 or Br, Q = anions of quinolin-8-ol (HQ 1) and its substituted species (HQ2)] from [OsX2Qz] (I) is described. The orange-red complexes are diamagnetic and exhibit v(NO) at ca. 1910 cm-1 in their i.r. spectra, indicating a high degree of nitrosonium ion (NO +) character. A single sharp Qz methyl signal is in line with the geometry of (2). The complexes display both spin-allowed and spin-forbidden charge transfer transitions in the 800 200 nm range. Chemical reactions toward nucleophiles, namely acetylacetone and propiophenone, clearly establish the electrophilic nature of the bound NO.
of osmium(III/IV)8-quinolinolates with Summary A group of mixed-tris chelates of type [OsAQ2 ] [A=isonitrosoacetophenonate (A ~) and isonitrosopropiophenonate (A2); Q = deprotonated 8-quinolinol (QI) and 2-methyl-8-quinolinol (Q2)] have been prepared by two distinct synthetic approaches. [OsAQ2] +, obtained by Ce Iv oxidation of [OsAQ2], can be regenerated by hydrazine hydrate reduction of the former. The complexes, characterized by physico-chemical, magnetic and spectroscopic methods, exhibit several spin-allowed and spin-forbidden charge transfer transitions in their electronic spectra. In MeCN solution the OsN30 3 unit displays a nearly-reversible OsW-Os m change and an Osm-Os" couple in the ca. -1.0-+0.3 V range versus s.c.e. The stability of the metal oxidation levels is discussed in terms of the chemical and electrochemical results.
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