Record Details

Electronic structure and catalytic aspects of [Ru(tpm)(bqdi)(Cl/H2O)](n), tpm = tris(1-pyrazolyl)-methane and bqdi = o-benzoquinonediimine

DSpace at IIT Bombay

View Archive Info
 
 
Field Value
 
Title Electronic structure and catalytic aspects of [Ru(tpm)(bqdi)(Cl/H2O)](n), tpm = tris(1-pyrazolyl)-methane and bqdi = o-benzoquinonediimine
 
Creator AGARWALA, H
EHRET, F
CHOWDHURY, AD
MAJI, S
MOBIN, SM
KAIM, W
LAHIRI, GK
 
Subject TRANSITION-METAL-COMPLEXES
ASYMMETRIC ALKENE EPOXIDATION
DENSITY-FUNCTIONAL THEORY
RUTHENIUM POLYPYRIDINE COMPLEXES
ACTIVE QUINONOID LIGANDS
CRYSTAL-STRUCTURE
REDOX PROPERTIES
HYDROGEN-PEROXIDE
OXIDATION-STATE
SPECTROELECTROCHEMICAL PROPERTIES
 
Description The diamagnetic complexes [Ru(tpm)(bqdi)(Cl)]ClO4 ([1]ClO4) (tpm = tris(1-pyrazolyl)methane, bqdi = o-benzoquinonediimine) and [Ru(tpm)(bqdi)(H2O)](ClO4)(2) ([2](ClO4)(2)) have been synthesized. The valence state-sensitive bond distances of coordinated bqdi [C-N: 1.311(5)/1.322(5) angstrom in [1]ClO4; 1.316(7)/1.314(7) angstrom in molecule A and 1.315(6)/1.299(7) angstrom in molecule B of [2](ClO4)(2)] imply its fully oxidised quinonediimine (bqdi(0)) character. DFT calculations of 1(+) confirm the {Ru-II-bqdi(0)} versus the anti-ferromagnetically coupled {Ru-III-bqdi()} alternative. The H-1 NMR spectra of [1]ClO4 in different solvents show variations in chemical shift positions of the NH (bqdi) and CH (tpm) proton resonances due to their different degrees of acidity in different solvents. In CH3CN/0.1 mol dm(-3) Et4NClO4, [1]ClO4 undergoes one reversible Ru-II reversible arrow Ru-III oxidation and two reductions, the reversible first electron uptake being bqdi based (bqdi(0)/bqdi()). The electrogenerated paramagnetic species {Ru-III-bqdi(0)}(1(2+)) and {Ru-II-Q()}(1) exhibit Ru-III-type (1(2+): < g > = 2.211/Delta g = 0.580) and radical-type (1: g = 1.988) EPR signals, respectively, as is confirmed by calculated spin densities (Ru: 0.767 in 1(2+), bqdi: 0.857 in 1). The aqua complex [2](ClO4)(2) exhibits two one-electron oxidations at pH = 7, suggesting the formation of {Ru-IV=O} species. The electronic spectral features of 1(n) (n = charge associated with the different redox states of the chloro complex: 2+, 1+, 0) in CH3CN and of 2(2+) in H2O have been interpreted based on the TD-DFT calculations. The application potential of the aqua complex 2(2+) as a pre-catalyst towards the epoxidation of olefins has been explored in the presence of the sacrificial oxidant PhI(OAc)(2) in CH2Cl2 at 298 K, showing the desired selectivity with a wide variety of alkenes. DFT calculations based on styrene as the model substrate predict that the epoxidation reaction proceeds through a concerted transition state pathway.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2014-10-17T05:59:29Z
2014-10-17T05:59:29Z
2013
 
Type Article
 
Identifier DALTON TRANSACTIONS, 42(10)3721-3734
http://dx.doi.org/10.1039/c2dt32402d
http://dspace.library.iitb.ac.in/jspui/handle/100/16128
 
Language en