Tolane-based phosphino- and arsino-ruthenium complexes in three different oxidation states

• Verfasst von: Rudin, Benjamin [VerfasserIn]
• Verfasst von: Stein, Carolin [VerfasserIn]
• Verfasst von: Ballmann, Joachim [VerfasserIn]
• Titel: Tolane-based phosphino- and arsino-ruthenium complexes in three different oxidation states
• Titelzusatz: Ru(I), Ru(II) and Ru(III)
• Verf.angabe: Benjamin Rudin, Carolin A. M. Stein, and Joachim Ballmann
• E-Jahr: 2025
• Jahr: 25 February 2025
• Umfang: 10 S.
• Illustrationen: Illustrationen, Diagramme
• Fussnoten: Gesehen am 08.04.2025
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Ort Quelle: Weinheim : Wiley-VCH, 1995
• Jahr Quelle: 2025
• Band/Heft Quelle: 31(2025), 12, Artikel-ID e202404546, Seite 1-10
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.202404546
• Datenträger: CD-ROM/DVD-ROM
• Sprache: eng
• Sach-SW: Alkynes
• Sach-SW: Arsane ligands
• Sach-SW: Phosphine ligands
• Sach-SW: Ruthenium
• Sach-SW: Thallium
• K10plus-PPN: 1921907630

Abstract

Targeting Ru(III) and Ru(I) η2-alkyne species, 2,2’-(iPr2E)2-substituted diphenylacetylenes (1-E, E=P, As) were employed for the preparation of [ECCE]-coordinated ruthenium complexes. The reactions between 1-E and cis-(MeCN)2(COD)RuCl2 led to the required Ru(II) starting materials cis-[ECCE]RuCl2(MeCN) (3-E). Upon oxidation of 3-E with PhICl2, the Ru(III) target complexes [ECCE]RuCl3 (7-E) were detectable for E=P and E=As, but only the arsa-derivative 7-As was obtained in a pure form, namely via oxidation of cis-[AsCCAs]RuCl2(THT) (THT=tetrahydrothiophene). Upon reduction 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 comprehensively 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.