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Ruthenium nitrosyl complexes with molecular framework [RuII(dmdptz)(bpy)(NO)]n+ (dmdptz: N,N-dimethyl-4,6-di(pyridin-2-yl)-1,3,5-triazin-2-amine and bpy: 2,2'-bipyridine). Electronic structure, reactivity aspects, photorelease, and scavenging of NO

Abstract

Two mononuclear ruthenium nitrosyl complexes with nitrogen rich ligand coordinated molecular framework [RuII(dmdptz)(bpy)(NO)]n+ (dmdptz: N,N-dimethyl-4,6-di(pyridin-2-yl)-1,3,5-triazin-2-amine and bpy: 2,2'-bipyridine), Enemark and Feltham notation {RuNO}6, [4]3+ (n = 3), and {RuNO}7, [4]2+ (n = 2), have been synthesized by sequential pathways from chloro precursor [RuII(dmdptz)(bpy)(Cl)]+ [1]+ via acetonitrile complex [RuII(dmdptz)(bpy)(CH3CN)]2+ [2]2+ and nitro complex [RuII(dmdptz)(bpy)(NO2)]+ [3]+. Single crystal X-ray structures of [1](ClO4) and [3](ClO4) have been successfully elucidated. Substantial low stretching frequency (NO) band of [4]3+ at 1914 cm due to influence of pyridyl-substituted s-triazine ligand which suggests the moderate electrophilic nature of NO. DFT calculated trans-angle (Ru1N6O1) of 176.713 and 141.745 in [4]3+ and [4]2+ indicate linear and bent coordination mode of NO to central ruthenium respectively. A noticeable shift of  (NO) (solid) ( = 364 cm1) has been observed on moving from [4]3+ to [4]2+ is well accused for NO centered one-electron reduction with {RuNO}6 to {RuNO}7 bonding alteration. The redox properties of [4]3+ have been studied with precursor complexes. Electrochemical conversion of [4]3+ to [3]+ has been performed in presence of 0.5 M NaOH solution. Both [4]3+ and [4]2+ facilitate photocleavage of RuNO bond on exposure with Xenon 200 W visible light source with first order rate constant kNO 8.44 x 10‒3 min‒1 (t1/2 = 82 min) and 4.64 x 10‒2 min‒1 (t1/2 = 15 min) respectively. Light triggered released NO has been captured by biological relevant target protein, reduced myoglobin as MbNO adduct.

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Supplementary files

Article information


Submitted
04 Aug 2020
Accepted
10 Oct 2020
First published
12 Oct 2020

New J. Chem., 2020, Accepted Manuscript
Article type
Paper

Ruthenium nitrosyl complexes with molecular framework [RuII(dmdptz)(bpy)(NO)]n+ (dmdptz: N,N-dimethyl-4,6-di(pyridin-2-yl)-1,3,5-triazin-2-amine and bpy: 2,2'-bipyridine). Electronic structure, reactivity aspects, photorelease, and scavenging of NO

S. Maji, B. Giri, S. Kumbhakar, K. Selvan K and A. Muley, New J. Chem., 2020, Accepted Manuscript , DOI: 10.1039/D0NJ03923C

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