NDLI: Synthesis and characterisation of ruthenium–nitrosyl complexes in oxygen-rich ligand environments

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Dalton Transactions Vol - 46 Issue - 3

Dalton Transactions Vol - 46 Issue - 2

Dalton Transactions Vol -39

Dalton Transactions Vol -0

Synthesis and characterisation of ruthenium–nitrosyl complexes in oxygen-rich ligand environments

Content Provider	Royal Society of Chemistry (RSC)
Author	Krishnan, V. Mahesh Tonzetich, Zachary J. Arman, Hadi D.
Copyright Year	2017
Abstract	A series of new {Ru–NO}6 complexes containing Kläui's tripodal oxygen ligand, [CpCo{P(O)(OMe)2}3]− (LOMe), and substituted catecholates have been prepared by chloride exchange with [Ru(LOMe)(NO)Cl2]. The [Ru(LOMe)(NO)(cat)] complexes (cat = dianion of catechol, 3,5-di-tert-butylcatechol, tetrabromocatechol, or 2,3-dihydroxynaphthalene) demonstrate spectroscopic features and redox properties consistent with the electronic character of the catecholate ligands. Several of the compounds display reversible oxidation events by cyclic voltammetry arising from the redox non-innocence of the catecholate ligands. Chemical oxidation of the di-tert-butylcatecholate complex, [Ru(LOMe)(NO)(tBu2cat)], with AgBF4 affords [Ru(LOMe)(NO)(tBu2semiquin)](BF4), a {Ru–NO}6 species that contains a semiquinone ligand. Photolysis of the semiquinone complex results in loss of NO and formation of the corresponding quinone complex, [Ru(LOMe)(CH3CN)(tBu2quin)](BF4). By contrast, photolysis of [Ru(LOMe)(NO)(Br4cat)], which contains the tetrabromocatecholate ligand, results in loss of NO and formation of the Ru(III) complex, [Ru(LOMe)(CH3CN)(Br4cat)]. Each of the new compounds represents a rare example of a Ru complex in an oxygen-rich ligand field, which may serve as a molecular model for heterogeneous catalysts comprising noble metal atoms dispersed on metal oxide supports.
Starting Page	1186
Ending Page	1193
Page Count	8
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	46
Issue Number	4
Journal	Dalton Transactions
DOI	10.1039/c6dt04717c
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Oxygen Ligand Chloride Cat Catechol Redox Cyclic voltammetry Silver tetrafluoroborate Semiquinone Photodissociation Quinone Acetonitrile Ligand field theory Molecular dynamics Noble metal
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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

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