Issue 42, 2015

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), Pri (4), But (5)]. Alternatively, the thionitrosyl complex 5 was obtained from [Bun4N][Ru(N)Cl4] and KN(But2PS)2, presumably via sulfur atom transfer from [N(But2PS)2] to the nitride. Reactions of 1 and 2 with NaLOEt (LOEt = [Co(η5-C5H5){P(O)(LOEt)2}3]) gave [Ru(NX)LOEtCl2] (X = S (8), Se (9)). Treatment of [Bun4N][Ru(N)Cl4] with KN(R2PS)2 produced RuIV–RuIV μ-nitrido complexes [Ru2(μ-N){N(R2PS)2}4Cl] [R = Ph (6), Pri (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 RuIII–RuIV μ-nitrido complex [Ru2(μ-N){N(But2PS)2}4] (10) that was oxidised by [Cp2Fe](PF6) to give the RuIV–RuIV complex [Ru2(μ-N){N(But2PS)2}4](PF6) ([10]PF6). The crystal structures of 1, 2, 3, 7, 9 and 10 have been determined.

Graphical abstract: Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands

Supplementary files

Article information

Article type
Paper
Submitted
02 Jul 2015
Accepted
23 Sep 2015
First published
24 Sep 2015

Dalton Trans., 2015,44, 18459-18468

Author version available

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

H. Ng, W. Cheung, E. Kwan Huang, K. Wong, H. H.-Y. Sung, I. D. Williams and W. Leung, Dalton Trans., 2015, 44, 18459 DOI: 10.1039/C5DT02513C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements