Tolane-Based Phosphino- and Arsino-Ruthenium Complexes in Three Different Oxidation States: Ru(I), Ru(II) and Ru(III).

IF 3.9 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemistry - A European Journal Pub Date : 2025-01-15 DOI:10.1002/chem.202404546

Benjamin Rudin, Carolin A M Stein, Joachim Ballmann

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引用次数: 0

Abstract

Targeting Ru(III) and Ru(I) η2-alkyne species, 2,2'-(iPr2E)2-substituted diphenylacetylenes (1-E, E = P, As) were em-ployed for the pre-paration of [ECCE]-coordinated ruthenium com-plexes. The re-actions between 1-E and cis-(MeCN)2(COD)RuCl2 led to the required Ru(II) starting materials cis-[ECCE]RuCl2(MeCN) (3-E). Upon oxi-dation of 3-E with PhICl2, the Ru(III) target com-plexes [ECCE]RuCl3 (7-E) were detectable for E = P and E = As, but only the arsa-deriva-tive 7-As was obtained in a pure form, namely via oxi-da-tion of cis-[AsCCAs]RuCl2(THT) (THT = tetrahydrothiophene). Upon re-duction of compounds 3-E, a hitherto unprecedented Ru(I) η2-alkyne complex, [PCCP]RuCl (9), was obtained for E = P. The former square planar Ru(I) complex (9) was characterized com-prehensively and examined in detail by means of DFT and CASSCF calculation. Upon treatment of 9 with TlPF6, a diamagnetic µ-Tl-bridged compound (10) with a nearly linear Ru-Tl-Ru array was formed and isolated in high yields. Careful analysis of the bonding situation suggested that the Ru-Tl-Ru moiety in 10 is best interpreted in terms of a 3c-4e- bond.

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来源期刊

Chemistry - A European Journal 化学-化学综合

CiteScore

7.90

自引率

4.70%

发文量

1808

审稿时长

1.8 months

期刊介绍： Chemistry—A European Journal is a truly international journal with top quality contributions (2018 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields. Based in Europe Chemistry—A European Journal provides an excellent platform for increasing the visibility of European chemistry as well as for featuring the best research from authors from around the world. All manuscripts are peer-reviewed, and electronic processing ensures accurate reproduction of text and data, plus short publication times. The Concepts section provides nonspecialist readers with a useful conceptual guide to unfamiliar areas and experts with new angles on familiar problems. Chemistry—A European Journal is published on behalf of ChemPubSoc Europe, a group of 16 national chemical societies from within Europe, and supported by the Asian Chemical Editorial Societies. The ChemPubSoc Europe family comprises: Angewandte Chemie, Chemistry—A European Journal, European Journal of Organic Chemistry, European Journal of Inorganic Chemistry, ChemPhysChem, ChemBioChem, ChemMedChem, ChemCatChem, ChemSusChem, ChemPlusChem, ChemElectroChem, and ChemistryOpen.