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Citation
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HERO ID
6919046
Reference Type
Journal Article
Title
Rhodium complexes of 3,5-di-tert-butylcatechol : synthesis, structure and, spectral and electrochemical properties
Author(s)
Sengupta, P; Bhattacharya, S; ,
Year
2013
Is Peer Reviewed?
Yes
Journal
Journal of the Indian Chemical Society
ISSN:
0019-4522
Publisher
SCIENTIFIC PUBL-INDIA
Location
JODHPUR
Volume
90
Issue
2
Page Numbers
169-179
Language
English
Web of Science Id
WOS:000209278900005
URL
https://www.scopus.com/inward/record.uri?eid=2-s2.0-84876392139&partnerID=40&md5=216e797b0a659f543c513dfb64c596eb
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Abstract
Reaction of [Rh(PPh3)(3)Cl] with 3,5-di-tert-butylcatechol (H2DBC) in dry benzene affords a bis-semiquinonato rhodium(III) complex, [Rh(PPh3)(DBSQ)(2)Cl]. A similar reaction of [Rh(PPh3)(3)Cl] with a mixture of H2DBC and quinolin-8-ol (Hq) in 1 : 1 : 1 mole ratio affords a mixed-his complex or rhodium(III), [Rh(PPh3)(DBSQ)(q)Cl]. Formation of complexes [Rh(PPh3)(DBSQ)(2)Cl] and [Rh(PBh(3))(DBSQ)(q)Cl] is delieved to proceed through the intermediacy of a reactive hydrido complex, generated in the initial step via oxidative insertion of rhodium into the acidic O-H fragment of the ligand. Reaction of H2DBC with RhCl3 center dot 3H(2)O in ethanol yields a tris-semiquinonato complex of rhodium(III), [Rh(DBSQ)(3)]. Formation of this [Rh(DBSQ)(3)] complex proceeds through simple displacement reaction. Structures of all the three complexes have been determined by X-ray crystallography. The [Rh(PPh3)(DBSQ)(2)Cl] complex is diamagnetic and shows characteristic H-1 NMR spectrum, while complexes [Rh(PPh3)(DBSQ)(q)Cl] and [Rh(DBSQ)(3)] are one-electron paramagnetic, and show sharp ESR signal with g similar to 2.0. All the complexes show intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry on all the three complexes shows an oxidation on the positive side of SCE and a reduction on the negative side, both of which are irreversible and ligand (DBSQ/q)-based.
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