Synthesis and spectro-electrochemical aspects of [RuII(trpy)(pdt)(X)]n+ (trpy = 2,2':6',2"-terpyridine, pdt = 5,6-Diphenyl-3-pyridyl-as-triazine, X = Cl-, CH3CN, NO2-, NO+, NO.) - electrophilicity of {RuII-NO+} and photolability of {RuII-NO.}

Maji, Somnath ; Chatterjee, Chandrani ; Mobin, Shaikh M. ; Lahiri, Goutam Kumar (2007) Synthesis and spectro-electrochemical aspects of [RuII(trpy)(pdt)(X)]n+ (trpy = 2,2':6',2"-terpyridine, pdt = 5,6-Diphenyl-3-pyridyl-as-triazine, X = Cl-, CH3CN, NO2-, NO+, NO.) - electrophilicity of {RuII-NO+} and photolability of {RuII-NO.} European Journal of Inorganic Chemistry, 2007 (21). pp. 3425-3434. ISSN 1434-1948

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/ejic.20...

Related URL: http://dx.doi.org/10.1002/ejic.200700143

Abstract

Nitrosylruthenium derivatives having NO+ and NO. states have been synthesized in a stepwise manner starting from [RuII(trpy)(pdt)(Cl)](ClO4) {[1](ClO4)} → [RuII(trpy)(pdt)(CH3CN)](ClO4)2 {[2](ClO4)2} → [RuII(trpy)(pdt)(NO2)](ClO4) {[3](ClO4)} → [RuII(trpy)(pdt)(NO+)](ClO4)3 {[4](ClO4)3} → [RuII(trpy)(pdt)(NO.)](ClO4)2 {[4](ClO4)2} [trpy = 2,2':6',2"-terpyridine, pdt = 5,6-diphenyl-3-pyridyl-as-triazine]. The molecular identity of [1](ClO4) and [2](ClO4)2 and the subsequent stereoretentive transformation of [1](ClO4) → [2](ClO4)2 have been authenticated by single-crystal X-ray structures. Electrochemical and spectral features are investigated as a function of the monodentate ligands (Cl-, CH3CN, NO2-, NO+, NO.). The kinetic and thermodynamic aspects of the reaction of the moderately strong electrophilic {RuII-NO+} center [ν(NO): 1944 cm-1] in [4]3+ with a nucleophile such as OH- have been studied. The nitrosyl species [RuII(trpy)(pdt)(NO+)]3+ ([4]3+) can be selectively reduced to [RuII(trpy)(pdt)(NO.)]2+([4]2+) electrochemically as well as chemically by hydrazine hydrate. On exposure to light an acetonitrile solution of [RuII(trpy)(pdt)(NO.)]2+ ([4]2+) undergoes slow photocleavage of the RuII-NO bond over a period of 4 h, resulting in the corresponding solvated species [RuII(trpy)(pdt)(CH3CN)]2+ ([2]2+). The rate of photolability of the RuII-NO bond in [4]2+has been monitored spectrophotometrically.

Item Type:Article
Source:Copyright of this article belongs to John Wiley and Sons, Inc.
Keywords:Ruthenium; Nitrosyl Complexes; Spectroscopy; Electrochemistry; Reactivity
ID Code:19133
Deposited On:23 Nov 2010 13:27
Last Modified:26 Feb 2011 04:13

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