Nachweis starker SH…︁S‐Brücken in [Ru(SH₂)(PPh₃)(′S₄′)]·THF, dem ersten röntgenographisch charakterisierten H₂S‐Komplex

Abstract

Welche Eigenschaften haben H2S‐Übergangsmetallkomplexe? Diese reaktiven Verbindungen spielen wahrscheinlich in vielen geochemischen und biologischen Prozessen eine wichtige Rolle. Bisher konnte aber kein derartiger Komplex vollständig charakterisiert werden. Beim Rutheniumkomplex 1 · THF, (′S4′)2⊖ = 2,2′‐(Ethylendithio)bis(thiophenolat), gelang nun eine Röntgenstrukturanalyse mit dem Ergebnis, daß der H2S‐Ligand durch überraschend starke SH …︁ S‐Brücken stabilisiert wird. An Luft wird 1 rasch zum (μ‐S2)‐Komplex 2 oxidiert [Gl. (a)].

Infrared Studies on the Interaction of Carbon Monoxide with Divalent Nickel in Hydrogenase from Chromatium vinosum

“…Interestingly, an unusually low v(S-H) at 2290 cm-l has been reported for a ruthenium complex exhibiting strong intermolecular S-H-43 bridges (Sellmann et al, 1991). Strong S-H-oH bridges with weak v(S-H) infrared absorbances at 2334 and 2375 cm-l have also been detected in a thiolate salt (Boorman et al, 1992).…”

In Quest of Competitive Catalysts for Nitrogenases and Other Metal Sulfur Enzymes

“…These may be detected and identified by coordination of CO yielding [Fe(CO)('S 4 ')] 2 (8) and [Fe(CO) 2 ('S 4 ')] (9). 18 Structure and reactivity of [Fe('S 4 ')] 4 reveal a caveat for the discussion of polynuclear [MS] enzyme centers. Such centers may dissociate and, as a consequence, may exhibit quite different structures in the resting and in the turnover state of the enzyme.…”

Half-Sandwich Ruthenium Phosphine Complexes with Sulfur-Donor Ligands. X-ray Crystal Structures of [Cp*RuH(SH)(PEt3)2][BPh4] and [Cp*Ru(S2COiPr)(PEt3)]

“…3 If H 2 S is considered, the interest arises not only because of its relevance to the biological sulfur cycle but also for its implication in the formation of ores and in hydrodesulfurization catalysis, as well as the potential use of H 2 S as a source of H 2 and organosulfur compounds. [4][5][6][7][8][9] However, there are very few examples of complexes containing coordinated H 2 S. 4,[10][11][12][13] Those reported are in general rather unstable and very reactive, and only in recent years have H 2 S complexes been unequivocally characterized by X-ray crystallography. 12,13 The first structure was reported by Sellmann and co-workers for the Ru II complex [Ru('S 4 ')(PPh 3 )-(SH 2 )]‚THF ('S 4 ' ) 1,2-bis[(2-mercaptophenol)thio]ethane), the crystal stability resulting from intermolecular H-bonding involving the THF solvate and strong S-H‚‚‚S bridging.…”

“…[4][5][6][7][8][9] However, there are very few examples of complexes containing coordinated H 2 S. 4,[10][11][12][13] Those reported are in general rather unstable and very reactive, and only in recent years have H 2 S complexes been unequivocally characterized by X-ray crystallography. 12,13 The first structure was reported by Sellmann and co-workers for the Ru II complex [Ru('S 4 ')(PPh 3 )-(SH 2 )]‚THF ('S 4 ' ) 1,2-bis[(2-mercaptophenol)thio]ethane), the crystal stability resulting from intermolecular H-bonding involving the THF solvate and strong S-H‚‚‚S bridging. 12 More recently, the crystal structure of the adduct [RuCl 2 (P-N)(PTol 3 )(SH 2 )]‚0.5 THF‚0.41H 2 O (P-N ) o-(diphenylphosphino)-N,N-dimethylaniline) has been reported, this being the first example of a structurally characterized transition metal-H 2 S complex formed under ambient conditions.…”