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• W2116718906 abstract "Abstract Reactions of the thiolate‐bridged diruthenium complex [Ru(py bu S 4 )] 2 ( 1 ) {py bu S 4 2− = 2,6‐bis[(3,5‐di‐ tert ‐butyl‐2‐sulfanylphenyl)thiomethyl]pyridine(2−)} with small‐molecule ligands L afforded the corresponding mononuclear complexes [Ru(L)(py bu S 4 )] [L = H − ( 2 ); CH 3 CN ( 3 ); NH 3 ( 4 ); CO ( 5 ); N 2 H 4 ( 6 ); PMe 3 ( 7 ); N 3 − ( 8 )]. The molecular structures of 3 , 4 , and 5 exhibit pseudooctahedral geometry with two thiolate and two thioether donor atoms in a trans configuration. Complexes 2 − 8 exhibit a quasi‐reversible, one‐electron redox wave of the Ru II /Ru III couple in the region between E 1/2 = +0.214 and +0.460 V vs. NHE. Complex 1 reacts reversibly with N 2 (60 bar) at 40 °C to give the labile dinitrogen complex [Ru(N 2 )(py bu S 4 )] ( 9 ). Complex 9 can also be obtained from the reaction between 3 and N 2 (20 bar) at room temperature. Treatment of 4 with NO afforded the labile 19‐valence‐electron species [Ru(NO)(py bu S 4 )] ( 10 ) in solution, which could subsequently be converted to 9 upon highpressure reaction with N 2 (20 bar). In contrast, the analogous reaction of 4 with NOBF 4 results in the formation of the oxidized complex [Ru(NH 3 )(py bu S 4 )]BF 4 ( 11 ), the structure of which was confirmed by X‐ray structure analysis. The carbonyl complex [Ru(CO)(py bu S 4 )] ( 5 ) could be reversibly protonated at the thiolate sulfur atom to give [Ru(CO)(py bu S 4 H)]BF 4 ( 12 ). UV irradiation of 5 and 12 under N 2 at −80 °C produced the short‐lived species 9 and 13 , respectively, which were identified spectroscopically. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)" @default.
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• W2116718906 date "2004-10-25" @default.
• W2116718906 modified "2023-10-11" @default.
• W2116718906 title "Reactivity of a Thiolate‐Bridged Dinuclear Ruthenium Complex with Nitrogenous Molecules: Spectroscopic Identification of a Labile Dinitrogen Complex" @default.
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• W2116718906 doi "https://doi.org/10.1002/ejic.200400375" @default.
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