Ruthenium nitrosyl complexes with the 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

Giri, Bishnubasu and Kumbhakar, Sadananda and Selvan K, Kalai and Muley, Arabinda and Maji, Somnath (2020) Ruthenium nitrosyl complexes with the 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. New Journal of Chemistry, 44 (43). pp. 18732-18744. ISSN 1144-0546

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Abstract

Two mononuclear ruthenium nitrosyl complexes with a 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 a chloro precursor [RuII(dmdptz)(bpy)(Cl)]+ [1]+via an acetonitrile complex [RuII(dmdptz)(bpy)(CH3CN)]2+ [2]2+ and a nitro complex [RuII(dmdptz)(bpy)(NO2)]+ [3]+. Single crystal X-ray structures of [1](ClO4) and [3](ClO4) have been successfully elucidated. A substantial low stretching frequency ν(NO) band of [4]3+ at 1914 cm-1 due to the influence of a pyridyl-substituted s-triazine ligand suggests the moderately electrophilic nature of NO. Density functional theory calculated trans-angles (Ru1-N6-O1) of 176.713° and 141.745° in [4]3+ and [4]2+ indicate linear and bent coordination modes of NO to central ruthenium, respectively. A noticeable shift in ν(NO) (solid) (Δν = 364 cm-1) which has been observed on moving from [4]3+ to [4]2+ is good evidence 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. The electrochemical conversion of [4]3+ to [3]+ has been performed in the presence of 0.5 M NaOH solution. Both [4]3+ and [4]2+ facilitate the photocleavage of the Ru-NO bond on exposure to a xenon 200 W visible light source with first-order rate constants kNO of 8.44 × 10-3 min-1 (t1/2 = 82 min) and 4.64 × 10-2 min-1 (t1/2 = 15 min), respectively. Light-triggered release of NO has been captured by a biologically relevant target protein, reduced myoglobin, as an Mb-NO adduct.

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IITH Creators:

IITH Creators	ORCiD
Giri, Bishnubasu	UNSPECIFIED
Kumbhakar, Sadananda	UNSPECIFIED
Selvan K, Kalai	UNSPECIFIED
Muley, Arabinda	UNSPECIFIED
Maji, Somnath	http://orcid.org/0000-0001-6047-1339

Item Type:

Article

Uncontrolled Keywords:

Acetonitrile complex; Electrochemical conversion; Electrophilic natures; First-order rate constants; Molecular frameworks; One-electron reductions; Single crystal x-ray structures; Stretching frequency

Subjects:

Chemistry
Chemical Engineering

Divisions:

Department of Chemistry

Depositing User:

. LibTrainee 2021

Date Deposited:

12 Jul 2021 05:08

Last Modified:

12 Jul 2021 05:08

URI:

http://raiithold.iith.ac.in/id/eprint/8231