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Revelation of Varying Coordination Modes and Noninnocence of Deprotonated 2,2 '-Bipyridine-3,3 '-diol in {Os(bpy)(2)} Frameworks

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Title Revelation of Varying Coordination Modes and Noninnocence of Deprotonated 2,2 '-Bipyridine-3,3 '-diol in {Os(bpy)(2)} Frameworks
 
Creator GHOSH, P
RAY, R
DAS, A
LAHIRI, GK
 
Subject DENSITY-FUNCTIONAL THEORY
NUCLEAR-MAGNETIC-RESONANCE
RAY CRYSTAL-STRUCTURES
ACID-BASE-EQUILIBRIUM
METAL-COMPLEXES
MIXED-VALENCY
RUTHENIUM(II) COMPLEXES
EXCITATION-ENERGIES
ELECTRON-TRANSFER
SENSING FEATURES
 
Description The reaction of 2,2'-bipyridine-3,3'-diol (H2L) and cis-Os-II(bpy)(2)Cl-2 (bpy = 2,2'-bipyridine) results in isomeric forms of [Os-II(bpy)(2)(HL-)]ClO4, [1]ClO4 and [2]ClO4, because of the varying binding modes of partially deprotonated HL-. The identities of isomeric [1]ClO4 and [2]ClO4 have been authenticated by their single crystal X-ray structures. The ambidentate HL- in [2]ClO4 develops the usual N,N bonded five-membered chelate with a strong O-H center dot center dot center dot O hydrogen bonded situation (O-H center dot center dot center dot O angle: 160.78 degrees) at its back face. The isomer [1]ClO4 however represents the monoanionic O-,N coordinating mode of HL-, leading to a six-membered chelate with the moderately strong O-H center dot center dot center dot N hydrogen bonding interaction (O-H center dot center dot center dot N angle: 148.87 degrees) at its backbone. The isomeric [1]ClO4 and [2]ClO4 also exhibit distinctive spectral, electrochemical, electronic structural, and hydrogen bonding features. The pK(a) values for [1]ClO4 and [2]ClO4 have been estimated to be 0.73 and
 
Publisher AMER CHEMICAL SOC
 
Date 2014-12-28T12:34:58Z
2014-12-28T12:34:58Z
2014
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 53(19)10695-10707
0020-1669
1520-510X
http://dx.doi.org/10.1021/ic501852a
http://dspace.library.iitb.ac.in/jspui/handle/100/16548
 
Language English