FULL PAPER Reactivity of 2-(Diphenylphosphanyl)thiophenol (HSC 6 H 4 PPh 2 ) with Ruthenium and Osmium Carbonyl Complexes; Breaking of HSC 6 H 4 PPh 2 into Sulfide, Phenyl and Diphenylphosphanyl Ligands on a Triruthenium Cluster Javier A. Cabezza,* [a] M. Angeles Martı ´nez-Garcı ´a, [a] Victor Riera, [a] Diego Ardura, [b] and Santiago Garcı ´a-Granda [b] Keywords: Ruthenium / Osmium / Phosphane-thiolate ligands / C-P activation / C-S bond activation 2-(Diphenylphosphanyl)thiophenol (HSC 6 H 4 PPh 2 ) reacts with the carbonyl clusters [Ru 3 (CO) 12 ] and [Os 3 (CO) 10 (MeCN) 2 ] to give mixtures of products, the composition of which depends upon the reaction conditions and the ratio of the reactants. The derivatives [M 3 (μ-H)(μ-η 2 - SC 6 H 4 PPh 2 )(CO) 9 ](1a: M = Ru; 1b: M = Os), [Ru 3 (μ 3 -S)(μ-η 2 - Ph)(μ-PPh 2 )(PPh 3 )(CO) 6 ] (2), and [Ru 2 (μ-η 2 - SC 6 H 4 PPh 2 ) 2 (CO) 4 ](3) have been isolated. The SC 6 H 4 PPh 2 ligand of compounds 1a and 1b has the sulfur atom spanning the same M-M edge as the hydride ligand and the Introduction The reactivity of unfunctionalized arenethiols with ru- thenium [1] [2] and osmium [3-7] carbonyl clusters has been studied in detail. Most of these investigations have at- tempted to shed light on the fundamental steps of catalytic hydrodesulfurization (HDS) reactions [8] in which sulfur is removed from thiols and other organosulfur compounds in fossil fuels. [9] However, despite the widespread use of HDS processes and their economic and environmental signifi- cance, the nature of the interaction of the organosulfur compounds with the catalysts and the mechanisms of the catalytic processes are still far from being well-known. [9] Both [Ru 3 (CO) 12 ] and [Os 3 (CO) 12 ] react with thiophenol to give [M 3 (μ-H)(μ-SPh)(CO) 10 ] (M = Ru, [2] Os [3] ) as pri- mary products. However, these compounds undergo facile C-S bond activation reactions, under thermal and/or pho- tochemical conditions, leading to the sulfide derivatives [M 3 (μ 3 -S)(μ 3 -CO)(CO) 9 ] (M = Ru, [2] Os [4] [5] ), [Os 3 (μ 3 - S) 2 (CO) 9 ], [3b,4,6] [M 3 (μ-H) 2 (μ 3 -S)(CO) 9 ] (M = Ru, [2] Os [4] ), [Ru 4 (μ 4 -S)(μ-CO) 2 (CO) 9 ] [2] [Os 4 (μ 3 -S) 2 (CO) 13 ], [3b] [Os 4 (μ 3 - S) 2 (CO) 12 ], [3b] and [Os 6 (μ 4 -S) 2 (CO) 17 ]. [5] It has also been re- ported that [Os 3 (CO) 11 (MeCN)] reacts with m- and p-thio- cresol to give [Os 3 (μ-H)(μ-SC 6 H 4 Me)(CO) 10 ] and that this reaction proceeds via the intermediate [Os 3 - (CO) 11 (HSC 6 H 4 Me)], in which both the sulfur and the hy- drogen atoms of the thiol group interact with an osmium atom. [7] [a] Departamento de Quı ´mica Orga ´nica e Inorga ´nica, Instituto de Quı ´mica Organometa ´lica “Enrique Moles,” Universidad de Oviedo, E-33071 Oviedo, Spain Fax: (internat.) + 34-985/103446 E-mail: jac@sauron.quimica.uniovi.es [b] Departamento de Quı ´mica Fı ´sica y Analı ´tica, Universidad de Oviedo, E-33071 Oviedo, Spain Eur. J. Inorg. Chem. 2000, 499-503  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000 1434-1948/00/0303-0499 $ 17.50+.50/0 499 phosphorus atom attached to one of the bridged metal atoms. Compound 2, which contains sulfide, phenyl, diphenylphosphanyl and triphenylphosphane ligands that arise from HSC 6 H 4 PPh 2 , has the Ru 3 triangle capped by the sulfide and two Ru-Ru edges spanned by bridging phenyl and diphenylphosphanyl ligands. In complex 3, the two SC 6 H 4 PPh 2 ligands have the same coordination behavior as in 1a or 1b; this binuclear complex is more conveniently prepared by treating [Ru 2 (μ-η 2 -MeCO 2 ) 2 (CO) 4 (MeCN) 2 ] with HSC 6 H 4 PPh 2 . Despite this interesting reactivity of thiophenols with ru- thenium and osmium carbonyl clusters, only a limited num- ber of studies involving functionalized thiophenols have been published. We have previously reported that 1,2- benzenedithiol reacts with [Ru 3 (CO) 12 ] and [Os 3 (CO) 12 ] to give the binuclear derivatives [M 2 (μ-η 2 -S 2 C 6 H 4 )(CO) 6 ] (M = Ru, Os), [10] and that treatment of 2-aminothiophenol with [Ru 3 (CO) 12 ] gives [Ru 3 (μ-H)(μ-η 2 -SC 6 H 4 NH 2 )- (CO) 9 ]. [11] However, the reaction of 2-aminothiophenol with [Os 3 (CO) 10 (MeCN) 2 ] gives [Os 3 (μ-H)(μ-SC 6 H 4 NH 2 )- (CO) 10 ], [12] in which the NH 2 group is not coordinated. It is also known that [Os 3 (CO) 10 (MeCN) 2 ] reacts with 2-mer- captobenzoic acid to give the hexanuclear compound [{Os 3 (μ-H)(CO) 10 } 2 (μ-η 3 -SC 6 H 4 CO 2 )], [13] in which the SC 6 H 4 CO 2 ligand connects two triangles of osmium atoms through the thiolate and the carboxylate groups, each group bridging one edge of the corresponding trimetal fragment. We report herein the reactivity of 2-(diphenylphos- phanyl)thiophenol (HSC 6 H 4 PPh 2 ) with [Ru 3 (CO) 12 ] and [Os 3 (CO) 10 (MeCN) 2 ]. Results and Discussion Treatment of a THF solution of [Ru 3 (CO) 12 ] with HSC 6 H 4 PPh 2 , in a 1:1 ratio, at reflux temperature for 1.5 h gave [Ru 3 (μ-H)(μ-η 2 -SC 6 H 4 PPh 2 )(CO) 9 ](1a) as the major component of a mixture of at least three products. The compound was isolated in 56% yield after a chromato- graphic workup. On the other hand, the osmium derivative [Os 3 (μ-H)(μ-η 2 -SC 6 H 4 PPh 2 )(CO) 9 ](1b) was isolated in 48% yield after a chromatographic separation from a mixture of at least four compounds, formed from the reaction of [Os 3 (CO) 10 (MeCN) 2 ] with HSC 6 H 4 PPh 2 , in a 1:1 ratio, in THF at room temperature.