Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands

Abstract

Ruthenium thio- and seleno-nitrosyl complexes containing chelating sulfur and oxygen ligands have been synthesised and their de-chalcogenation reactions have been studied. The reaction of mer-[Ru(N)Cl3(AsPh3)2] with elemental sulfur and selenium in tetrahydrofuran at reflux afforded the chalcogenonitrosyl complexes mer-[Ru(NX)Cl3(AsPh3)2] [X = S (1), Se (2)]. Treatment of 1 with KN(R2PS)2 afforded trans-[Ru(NS)Cl{N(R2PS)2}2] [R = Ph (3), Pr(i) (4), Bu(t) (5)]. Alternatively, the thionitrosyl complex 5 was obtained from [Bu(n)4N][Ru(N)Cl4] and KN(Bu(t)2PS)2, presumably via sulfur atom transfer from [N(Bu(t)2PS)2](-) to the nitride. Reactions of 1 and 2 with NaLOEt (LOEt(-) = [Co(η(5)-C5H5){P(O)(LOEt)2}3](-)) gave [Ru(NX)LOEtCl2] (X = S (8), Se (9)). Treatment of [Bu(n)4N][Ru(N)Cl4] with KN(R2PS)2 produced Ru(IV)-Ru(IV)μ-nitrido complexes [Ru2(μ-N){N(R2PS)2}4Cl] [R = Ph (6), Pr(i) (7)]. Reactions of 3 and 9 with PPh3 afforded 6 and [Ru(NPPh3)LOEtCl2], respectively. The desulfurisation of 5 with [Ni(cod)2] (cod = 1,5-cyclooctadiene) gave the mixed valance Ru(III)-Ru(IV)μ-nitrido complex [Ru2(μ-N){N(Bu(t)2PS)2}4] (10) that was oxidised by [Cp2Fe](PF6) to give the Ru(IV)-Ru(IV) complex [Ru2(μ-N){N(Bu(t)2PS)2}4](PF6) ([10]PF6). The crystal structures of 1, 2, 3, 7, 9 and 10 have been determined.

A Selective and Cell-Permeable Mitochondrial Calcium Uniporter (MCU) Inhibitor Preserves Mitochondrial Bioenergetics after Hypoxia/Reoxygenation Injury

“…Relevant interatomic distances and angles as well as details for the crystal structure refinement of C-2 and C-3 are shown in Tables S1–S3 (SI). The Ru–N distances of the nitrido bridge agree well with previously synthesized compounds. ,− The NH 3 ligands of the bridged Ru IV centers of C-2 are arranged in an eclipsed configuration, whereas the ethylenediamine ligands of C-3 crystallize in a staggered conformation. This disparity may indicate that the rotation about the Ru–N–Ru axis is facile.…”

Tetranuclear Ruthenium Cyclopentadienyl and Pentamethylcyclopentadienyl Complexes Containing Bridging Nitrido Ligands

“…Attempts have been made to synthesize Cp*Ru­(IV) nitride complexes using other Ru­(VI) terminal nitrido starting materials. In particular, the reaction with the Ru­(VI) nitride mer -[Ru­(N)­Cl 3 (AsPh 3 ) 2 ], which has been shown to display electrophilic behavior, was studied . Treatment of [Cp*Ru­(MeCN) 3 ]­(PF 6 ) with mer -[Ru VI (N)­Cl 3 (AsPh 3 ) 2 ] in THF/CH 2 Cl 2 afforded air-stable dark red crystals that were identified as the tetranuclear μ-nitrido complex [{Cp*Ru­(μ-N)­RuCl­(AsPh 3 )} 2 (μ-Cl) 4 (μ-O 2 PF 2 )]­(PF 6 ) ( 5 ) (Scheme ).…”

Ruthenium-nitrosyl complexes as NO-releasing molecules, potential anticancer drugs, and photoswitches based on linkage isomerism

“…Thio-, Seleno-, and Telluronitrosyl (E = S, Se, Te). Ruthenium thionitrosyl complexes can be synthesized by: (a) sulfur atom transfer to ruthenium(VI) nitrido species, 84,85 (b) reaction of ruthenium(III) complexes with trithiazyl chloride (N 3 S 3 Cl 3 ), 86 (c) halide abstraction from thiazyl complexes, and (d) reaction of tetrasulfur tetranitride (S 4 N 4 ) with metal halides or nitrides. 87 Selenonitrosyl complexes can be prepared by treatment of ruthenium nitride species with elemental selenium.…”

“…, where E = S, Se (Scheme 2). 84 The complex [RuCl 2 (NS)(L OEt )] was also prepared in 70% yield by reaction of electrophilic ruthenium(VI)…”

“…87 Selenonitrosyl complexes can be prepared by treatment of ruthenium nitride species with elemental selenium. 84 In contrast to NO, the chemistry of heavier congeners NS (nitric sulfide), NSe (nitric selenide) and NTe (nitric telluride), as well as of HNO, has gained much less attention. This is because these are elusive molecules; the NE species can be detected only at low temperatures.…”