Synthesis and reactivity of mono-, tri-, and poly-nuclear ruthenium carbonyl complexes containing the pyridine-2-thiolate ligand (pyS). Stepwise preparation of [Ru(pyS)₂(CO)₂] by reaction of [Ru₃(CO)₁₂] with pyridine-2-thiol

Abstract

The thermal reaction of [ Ru,( CO),,] with pyridine-2-thiol (pySH) gives the trinuclear complex [R~,(p-H)(p,-pyS)(C0)~] (I), which is subsequently converted into the polymer [{Ru(p,-pyS) (CO),},](2). Further reaction of polymer (2) with pyridine-2-thiol gives the monomeric compound [Ru(pyS),(CO),](3). Complexes (1) and (2) contain triply bridging pyS ligands while in complex (3) both pyS ligands are chelating. These results indicate that the reactivity of [Ru,(CO),,] with pyridine-2-thiol is different to that found for [Os,(CO),,] and for [Ru,(CO),,]with 2-aminopyridine and 2-hydroxypyridine. The reactions of complexes (I )-(3) with several P-donor ligands are also described. Infrared and l H and 31P-{1H} n.m.r. spectral data for all the compounds are presented and discussed in relation to their structures.It is well known that the deprotonated derivatives of 2aminopyridine, 2-hydroxypyridine, and pyridine-2-thiol (pySH) are ligands that give related complexes with many different metals.'-4 The three ligands have been studied in reactions with [Os,(CO), ,] and although their behaviour is not completely alike, it is very However, in a recent paper, we have reported the very different reactivity of 2-aminopyridine and 2hydroxypyridine with [RU,(CO),,].~ In view of these data we decided to investigate the reactions of pyridine-2-thiol with [RU~(CO)~,]. Here we describe that chemistry as well as the reactivity of the products obtained with several P-donor ligands. Results and Discussion Complexes(1)-(3)-The reaction of [ R U ~( C O ) ~, ] with pySH, in a 1 : 3 mol ratio, in refluxing toluene for 1 h, gave rise to the precipitation of the brick-red polymer [{ Ru(p,-pyS)-(CO),},] (2) (Scheme). However, a transient intermediate was detected during the first 10 min by monitoring the reaction with

Synthesis, spectroscopic characterization and DFT study of dinuclear ruthenium sawhorse-type complexes derived from the reaction of trinuclear aggregates and (Z)-5-arylidenerhodanines

“…The HOMO is mainly located on the Ru-S bond that coordinates a monomeric fragment with another and on the Ru (2) because the fragmentation of the metallic aggregate is more important than substitution and oxidative addition reactions. These results are in agreement with the experimental work reported by Cabeza and co-workers [16,17]. To gain insight into each of the steps that give origin to the sawhorse structures we carried out in section 4.3 a proposed DFT-mechanism of the fragmentation reaction.…”

“…Other sawhorse type polymers [Ru 2 (CO) 4 (μ-Xpy) 2 ] n 7a-b (figure 2) have been obtained from reaction between [Ru 3 (CO) 12 ] and 2-hydroxy (OHPy) [16] and 2-mercapto-pyridine (SHPy) [17] as yellow and red solids, respectively. Reaction with 2-hydroxypyridine showed the presence of [Ru 4 H 4 (CO) 12 ] and [Ru 2 (CO) 4 (OHPy) 2 (µ-OPy) 2 ] [18] 8a and the reaction with 2-mercaptopyridine presented secondary product, the mononuclear [Ru(CO) 2 (SPy) 2 ].…”

A new coordination mode for (pyrid-2-yl)thiolate (L) ligands: Synthesis and characterization of [Ru6(μ3-H)(μ5-κ2-L)(μ-CO)(CO)15]

“…The (pyrid-2-yl)thiolate ligand has been found to be very versatile, being able to bind metal atoms in a monodentate manner through the sulfur atom [13], as a chelating ligand [7,13], as a bridging ligand through both nitrogen and sulfur and through sulfur alone [14], as a triply-bridging ligand [7,15] and as a quadruply-bridging ligand [8]. The quintuply-bridging coordination mode of the (pyrid-2-yl)thiolate ligands of 1 and 2 is unprecedented.…”

“…Our group has described that the thermal treatment of these two reagents, in a 1:1 mole ratio, leads to [Ru 3 (l-H)(l 3 -j 2 -Spy)(CO) 9 ]. This trinuclear cluster reacts further with more HSpy to give, sequentially, the polymeric material [{Ru 2 -(l 3 -j 2 -Spy) 2 (CO) 4 } n ] and the monomeric complex [Ru-(j 2 -Spy) 2 (CO) 2 ] (Scheme 2) [7]. Deeming's group has reported that [Ru 3 (l-H)(l 3 -j 2 -Spy)(CO) 9 ] is thermally unstable, undergoing trimerization in refluxing cyclohexane to give [{Ru 3 (l 3 -H)(l 4 -j 2 -Spy)(CO) 7 } 3 ] (Scheme 2) [8].…”

Sawhorse-type diruthenium tetracarbonyl complexes

“…14), which dissolves in boiling acetonitrile to give the dinuclear complex Ru 2 (CO) 4 (Opy) 2 (NCMe) 2 [53]. The analogous reaction with pyridine-2-thiol (pySH) gives the bispyridylthiolato-bridged polymer [Ru 2 (CO) 4 (Spy) 2 ] n [54].…”