Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands. Issue 42 (7th October 2015)

• Record Type: Journal Article
• Authors: Ng, Ho-Yuen; Cheung, Wai-Man; Kwan Huang, Enrique; Wong, Kang-Long; Sung, Herman H.-Y.; Williams, Ian D.; Leung, Wa-Hung
• Is Part Of: Dalton transactions. Volume 44:Issue 42(2015)
• Page Start: 18459
• Page End: 18468
• Publication Date: 2015-10-07
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt02513c
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Ruthenium thio- and seleno-nitrosyl complexes containing chelating sulfur and oxygen ligands have been synthesised and their de-chalcogenation reactions have been studied. 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 of1 with KN(R2 PS)2 afforded trans -[Ru(NS)Cl{N(R2 PS)2 }2 ] [R = Ph (3 ), Pr i (4 ), Bu t (5 )]. Alternatively, the thionitrosyl complex5 was obtained from [Bu n 4 N][Ru(N)Cl4 ] and KN(Bu t 2 PS)2, presumably via sulfur atom transfer from [N(Bu t 2 PS)2 ] − to the nitride. Reactions of1 and2 with NaLOEt (LOEt − = [Co(η 5 -C5 H5 ){P(O)(LOEt )2 }3 ] − ) gave [Ru(NX)LOEt Cl2 ] (X = S (8 ), Se (9 )). Treatment of [Bu n 4 N][Ru(N)Cl4 ] with KN(R2 PS)2 produced Ru IV –Ru IV μ-nitrido complexes [Ru2 (μ-N){N(R2 PS)2 }4 Cl] [R = Ph (6 ), Pr i (7 )]. Reactions of3 and9 with PPh3 afforded6 and [Ru(NPPh3 )LOEt Cl2 ], respectively. The desulfurisation of5 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 2 PS)2 }4 ] (10 ) that was oxidised by [Cp2 Fe](PF6 ) to give the Ru IV –Ru IV complex [Ru2 (μ-N){N(Bu t 2 PS)2 }4 ](PF6 ) ([10 ]PF6 ). The crystal structures of1, 2, 3, 7, 9 and10 have been determined.