Document Type

Journal Article

Department/Unit

Department of Chemistry

Title

Synthesis, structures and reactivity of ruthenium nitrosyl complexes containing Kläui's oxygen tripodal ligand

Language

English

Abstract

Ruthenium nitrosyl complexes containing the Kläui's oxgyen tripodal ligand LOEt - ([CpCo{P(O)(OEt)2} 3]- where Cp = η5-C5H 5) were synthesized and their photolysis studied. The treatment of [Ru(NN)(NO)Cl3] with [AgLOEt] and Ag(OTf) afforded [L OEtRu(NN)(NO)][OTf]2 where NN = 4,4′-di-tert-butyl- 2,2′-bipyridyl (dtbpy) (2·[OTf]2), 2,2′-bipyridyl (bpy) (3·[OTf]2), N,N,N′N′- tetramethylethylenediamine (4·[OTf]2). Anion metathesis of 3·[OTf]2 with HPF6 and HBF4 gave 3·[PF6]2 and 3·[BF4]2, respectively. Similarly, the PF6 - salt 4·[PF 6]2 was prepared by the reaction of 4·[OTf] 2 with HPF6. The irradiation of [LOEtRu(NO) Cl2] (1) with UV light in CH2Cl2-MeCN and tetrahydrofuran (thf)-H2O afforded [LOEtRuCl 2(MeCN)] (5) and the chloro-bridged dimer [LOEtRuCl] 2(μ-Cl)2 (6), respectively. The photolysis of complex [2][OTf]2 in MeCN gave [LOEtRu(dtbpy)(MeCN)][OTf] 2 (7). Refluxing complex 5 with RNH2 in thf gave [L OEtRuCl2(NH2R)] (R = tBu (8), p-tol (9), Ph (10)). The oxidation of complex 6 with PhICl2 gave [L OEtRuCl3] (11), whereas the reduction of complex 6 with Zn and NH4PF6 in MeCN yielded [LOEtRu(MeCN) 3][PF6] (12). The reaction of 3·[BF 4]2 with benzylamine afforded the μ-dinitrogen complex [{LOEtRu(bpy)}2(μ-N2)][BF4] 2 (13) that was oxidized by [Cp2Fe]PF6 to a mixed valence RuII,III species. The formal potentials of the RuL OEt complexes have been determined by cyclic voltammetry. The structures of complexes 5,6,10,11 and 13 have been established by X-ray crystallography. © 2011 The Royal Society of Chemistry.

Publication Date

2011

Source Publication Title

Dalton Transactions

Volume

40

Issue

41

Start Page

11043

End Page

11050

Publisher

Royal Society of Chemistry

DOI

10.1039/c1dt10306g

Link to Publisher's Edition

http://dx.doi.org/10.1039/c1dt10306g

ISSN (print)

14779226

ISSN (electronic)

14779234

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