Record Details

Effect of 2-(2-pyridyl)azole-based ancillary Ligands (L1-4) on the electrophilicity of the nitrosyl function in [Ru-II(trpy)(L1-4)(NO)](3+) [trpy=2,2 ': 6 ',2 ''-terpyridine]. Synthesis, structures, and spectroscopic, electrochemical, and kinetic aspects

DSpace at IIT Bombay

View Archive Info
 
 
Field Value
 
Title Effect of 2-(2-pyridyl)azole-based ancillary Ligands (L1-4) on the electrophilicity of the nitrosyl function in [Ru-II(trpy)(L1-4)(NO)](3+) [trpy=2,2 ': 6 ',2 ''-terpyridine]. Synthesis, structures, and spectroscopic, electrochemical, and kinetic aspects
 
Creator CHANDA, N
PAUL, D
KAR, S
MOBIN, SM
DATTA, A
PURANIK, VG
RAO, KK
LAHIRI, GK
 
Subject dna-binding properties
ray crystal-structure
nitric-oxide
ruthenium complexes
spectroelectrochemical properties
terpyridine complexes
polypyridyl complexes
electron-transfer
molecular-structure
reversible binding
 
Description Ruthenium nitrosyl complexes [Ru(trpy)(L1-4)(NO)](3+) (13-16) [trpy = 2,2':6',2"-terpyridine, L-1 = 2-(2-pyridyl)-benzoxazole, L-2 = 2-(2-pyridyl)benzthiazole, L-3 = 2-(2-pyridyl)benzimidazole, L-4 = 1-methyl-2-(2-pyridyl)-1H-benzimidazole] were obtained in a stepwise manner starting from [Ru-II(trpy)(L1-4) (Cl)]ClO4 (1-4) → [Ru-II(trpy)(L1-4) (H2O)](ClO4)(2) (5-8) → [Ru-II(trpy)(L1-4) (NO2)ClO4 (9-12) → [Ru-II(trpy)(L-1,L-2,L-4) (NO)](ClO4)(3) (13, 14, 16)/[Ru-II(trpy)(L-3) (NO)](Cl)(4))(2)(NO3) (15). Crystal structures of 1, 2, 4, 9, 12, 13, 15, and 16 established the stereoretentive nature of the transformation processes. Though the complexes of L1, L3, and L 4 were isolated in the isomeric form A (π-acceptor trpy and azole ring in the equatorial plane and the pyridine and chloride donors in the axial positions), complexes of L 2 preferentially stabilized in form B (trpy and pyridine in the equatorial plane and the azole ring and chloride donors in the axial positions). The v(NO) stretching frequency varied in the range of 1957-1932 cm(-1), 13 &MGT; 14 &MGT; 15 > 16, primarily depending on the electronic aspects of L as well as the isomeric structural forms. The coordinated nitrosyl function underwent successive reductions of [Ru-II-NO+](3+) → [Ru-II-NO•](2+) and [Ru-II-NO•](2+) - [Ru-II-NO-](+), and the first reduction potential follows the order 14 > 13 &MGT; 15 ≈ 16. The nearly axial EPR spectra having nitrogen hyperfine splittings (A ≈ 26 G) at 77 K of 13(-)-16(-) with (g) ≈ 2.0 established that the reduction process is largely centered around the nitrosyl function. Despite an appreciably high v(NO), the complexes were found to be unusually stable even in the aqueous medium. They transformed slowly and only partially into the corresponding nitro derivatives in H2O (k ≈ 10(-4) s(-1) and K = 0.4-3.8). The chloro (1-4), aqua (5-8), and nitro (9-12) derivatives displayed reasonably strong emissions near 700 nm at 77 K (φ = 10(-1)-10(-2)). The aqua derivative 7 was found to interact with the calf thymus and the circular form of p-Bluescript SK DNA.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-14T00:01:57Z
2011-12-26T12:47:27Z
2011-12-27T05:34:28Z
2011-07-14T00:01:57Z
2011-12-26T12:47:27Z
2011-12-27T05:34:28Z
2005
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 44(10), 3499-3511
0020-1669
http://dx.doi.org/10.1021/ic048184w
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3805
http://hdl.handle.net/10054/3805
 
Language en