Addition von Schwefeldioxid an Ruthenium-Thiolat-Komplexe, Struktur eines bemerkenswert stabilen Thiolat-SO₂-Addukts [1]/ Addition of Sulfur Dioxide to Ruthenium Thiolate Complexes, Structure of a Remarkably Stable Thiolate-SO₂-Addukt [1]

Abstract

Ruthenium thiolates [cpRu(PPh3),(SMe)] and [cp*Ru(PPh2Me)2(SR)] (R = Me, Ph) react with sulfur dioxide in two different ways, substitution of phosphine for SO2, and addition of SO2 to the thiolate ligand. The structure of [cpRu(CO)(PPh3)(SMe · SO2)] was determined by X-ray crystallography: Crystals are monoclinic, space group P21/n, a = 10.26(9), b = 16.00(6), c = 14.73(6) Å, β = 90.141(5)°, Ζ = 4. The most remarkable feature is a very long (247,8 pm) S—S single bond. [cp*Ru(PPh2Me)(SO2)(SPh)] and the corresponding sulfur monoxide complex [cp*Ru(PPh2Me)(SO)(SPh)] undergo [3+2] cycloaddition with dimethylacetylene-dicarboxylate.

Microwave Accelerated Synthesis of Cyclopentadienyl Bis-Phosphine Ruthenium (II) Thiolato Complexes Using Focused Microwave Irradiation

“…Bis-(triphenylphosphine)-thiolato complexes 2 have been synthesised thermally by reaction of chloro complex 1 with the appropriate sodium thiolate in an ethanol/THF mixture. [6][7][8] The reaction time for completion of the reaction is 2 h and additional PPh 3 is added to the reaction mixture to avoid formation of cubane type thiolate clusters [6][7][8] While the yield of compound 2 is excellent under thermal conditions under microwave irradiation (100 W, 60s, in diethylene glycol) a mixture of at least five compounds could be detected by NMR. The desired compound 2 was formed in 20% yield.…”

“…The side products are presumably ruthenium clusters with bridged thiolate ligands, but these could not be adequately characterised due to difficulties in the separation procedure. [6][7][8] Next we turned our attention to the more stable bisdiphenylphophinomethane (dppm) thiolato complexes 3a-e, which contain a chelating phosphine ligand. Again under thermal conditions the reaction is complete after 2 h reflux in an ethanol/THF solvent mixture and the compounds are obtained in excellent yield.…”

“…9 Compounds 3a and 3b have been described in the literature. 7 Compounds 3c-e are new compounds. The new thiolato-complexes are moderately air sensitive yellow powders, which are soluble in benzene, toluene, acetone and other polar solvents.…”

“…The 31 P-NMR spectrum shows a singlet in the expected area. 6,7 The thiolate α-CH signals in the 1 H and 13 C NMR spectrum are only marginally shifted in comparison to the free ligand. The coordination of the thiolate to the metal centre can be easily deduced from the 13 C NMR spectra of the complexes, which appears as a triplet and exhibit a 3 J PRuSC coupling of 7 Hz to the α-C.…”

The coordination chemistry of small sulfur-containing molecules: a personal perspective

“…14. 43 Analogous metal carbonyls show similar reactivity. 44 More reactions of sulfur dioxide complexes will be discussed below.…”