Aktivierung von Schwefelkohlenstoff an Trirutheniumclustern: Synthese und Kristallstruktur von [Ru3(CO)4(μ-PCy2)2(μ-Ph2PCH2PPh2)(μ3-S){μ3-η2-CSC(S)S}]

Abstract

Ru 3 (CO) 4 (µ-H) 3 (µ-PCy 2 ) 3 (µ-dppm)] (2) (dppm ϭ Ph 2 PCH 2 PPh 2 ) reacts with CS 2 at room temperature and yields the open 50 valence electron cluster [Ru 3 (CO) 4 (µ-PCy 2 ) 2 (µ-dppm)-(µ 3 -S){µ 3 -η 2 -CSC(S)S}] (3) containing the unusual µ 3 -η 2 -C 2 S 3 mercaptocarbyne ligand. Compound 3 was characterized by single crystal X-ray structure analysis.

Carbonyl substitution chemistry of some trimetallic transition metal cluster complexes with polyfunctional ligands

“…The overall structure adopted by [Ru 3 (CO) 5 (dppm)(l 2 -PMe(C 6 H 4 CH 2 OMe)) 4 ] (6), appears to be unique with no examples of a trinuclear, open-triangular cluster that contains six phosphine/phosphide donors found in the CSD [30]. The individual phosphides bridge the metal-metal bonds, a motif that is well known in the literature [32][33][34][35][36][37][38][39][40]. Much more common is a motif in which a triruthenium cluster has each Ru-Ru vector symmetrically bridged by phosphides, as exemplified by [Ru 3 (CO) 9 (l-H)(l-P(C 6 H 11 ) 2 ) 3 ] [38].…”

Fe(CO)5 promoted C–S bond activation and formation of an unusual C2S3 ligand in [{Fe2(CO)6}2(μ-C2S3)]

“…When a solution of Fe(CO) 5 and CS 2 in hexane was photolyzed for 30 min at 0°C, the novel cluster [{Fe 2 (CO) 6 } 2 (l-C 2 S 3 )] (1) (10%) was isolated after chromatographic work-up (Scheme 1), along with known Fe 3 S 2 (CO) 9 (9%) and Fe 2 S 2 (CO) 6 (9%). The yield of 1 did not improve when CS 2 was used as the solvent in the photolysis reaction.…”

“…Although the exact mechanism of formation of 1 is not known, investigation of reactions of Ru(CO) 5 , Mo(CO) 6 and W(CO) 6 with CS 2 under similar reaction conditions do not yield analogs of 1. Formally, two molecules of CS 2 must react, with one of them formally undergoing the loss of a sulfur atom.…”

“…The low temperature photochemical reaction of Fe(CO) 5 and CS 2 leads to desulfurization and formation of an unusual C 2 S 3 ligand containing a C@C double bond in the complex [{Fe 2 (CO) 6 } 2 (l-C 2 S 3 )]. Activation of C@S bond is selective for the reaction with Fe(CO) 5 .…”

“…CS 2 has been shown to undergo a variety of reactions with transition metals, including insertion [1,2] and disproportionation [3][4][5], and there is a growing interest in the activation of CS 2 from catalytic and biological points of view. Cleavage of both C@S bonds of CS 2 is predicted to be exothermic process [6].…”