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Electronic structures and reactivity aspects of ruthenium-nitrosyls

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Title Electronic structures and reactivity aspects of ruthenium-nitrosyls
 
Creator DE, P
MONDAL, TK
MOBIN, SM
LAHIRI, GK
 
Subject NO-CENTER-DOT
DENSITY-FUNCTIONAL THEORY
NITRIC-OXIDE
REDOX PROPERTIES
ELECTROPHILIC REACTIVITY
PHOTODYNAMIC THERAPY
MOLECULAR-STRUCTURE
ANCILLARY LIGANDS
CRYSTAL-STRUCTURE
VISIBLE-LIGHT
Ruthenium
Nitrosyl
Electrochemistry
Spectra
DFT
Photocleavage
 
Description Nitrosyl complexes with {Ru-NO}(6) (4(ClO(4))(3)) and {Ru-NO}(7) (4(ClO(4))(2)) configurations have been isolated in the selective molecular framework of [Ru(tpm)(pap)(NO)](n+) (tpm = tris(1-pyrazolyl) methane and pap = 2-phenylazopyridine). The DFT optimized structures of [Ru(II)(tpm)(pap)(NO(+))](3+) (4(3+)) and [Ru(II)(tpm)(pap)(NO(center dot))](2+) (4(2+)) predict that the Ru-N-O groups in the complexes are in almost linear and bent geometries, respectively. In agreement with largely NO centered reduction a sizeable shift in m(NO) frequency of 324 cm (1) has been observed on moving from {Ru(II)-NO(+)} state in 4(3+) to {Ru(II)-NO(center dot)) state in 4(2+). The DFT proposed NO centered spin in {Ru(II)-NO(center dot)) (4(2+)) (Mulliken spin-densities: 0.860 (NO) and 0.087 (Ru)) has been evidenced by its free radical EPR spectrum with g = 1.989. The strongly electrophilic {Ru(II)-NO(+)} state in 4(3+) (m(NO): 1962 cm (1)) can be transformed to the corresponding {Ru(II)-NO(2) } complex (3(+)) in the presence of nucleophile, OH with k = 2.03 x 10 (1) M (1) s (1) at 298 K in CH(3)CN. On irradiation with light the acetonitrile solution of [Ru(II)(tpm)(pap)(NO(+))](3+) (4(3+)) undergoes facile photorelease of NO (k(NO), s (1) = 0.1 x 10 (1) and t(1/2), s = 69.3) with the concomitant formation of the solvate [Ru(II)(tpm)(pap)(CH(3)CN)](2+) (2(2+)). The photoreleased NO can be trapped as an Mb-NO adduct. (C) 2011 Elsevier B.V. All rights reserved.
 
Publisher ELSEVIER SCIENCE SA
 
Date 2012-06-26T06:46:54Z
2012-06-26T06:46:54Z
2011
 
Type Article
 
Identifier INORGANICA CHIMICA ACTA,372(1)250-258
0020-1693
http://dx.doi.org/10.1016/j.ica.2011.01.077
http://dspace.library.iitb.ac.in/jspui/handle/100/14074
 
Language English