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Updated: Jun 2, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Tolane-Based Phosphino- and Arsino-Ruthenium Complexes in Three Different Oxidation States: Ru(I), Ru(II) and Ru(III)
Benjamin Rudin1, Carolin A M Stein1, Joachim Ballmann1
1Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 276, D-69120, Heidelberg, Germany.
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.
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