Tolane-based phosphino- and arsino-ruthenium complexes in three different oxidation states: Ru(I), Ru(II) and Ru(III)
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(Me...
Saved in:
| Main Authors: | , , |
|---|---|
| Format: | Article (Journal) |
| Language: | English |
| Published: |
25 February 2025
|
| In: |
Chemistry - a European journal
Year: 2025, Volume: 31, Issue: 12, Pages: 1-10 |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.202404546 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/chem.202404546 Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.202404546 
|
| Author Notes: | Benjamin Rudin, Carolin A. M. Stein, and Joachim Ballmann |
| Summary: | 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. |
|---|---|
| Item Description: | Gesehen am 08.04.2025 |
| Physical Description: | CD/DVD/Blu-ray |
| ISSN: | 1521-3765 |
| DOI: | 10.1002/chem.202404546 |