Complex Reduction Chemistry of (abpy)PtCl2, abpy = 2,2'-Azobispyridine: Formation of Cyclic (m,h2:h1-abpy)PtCl22+ with a New Coordination Mode for abpy and a Near-Infrared Ligand-to-Ligand Intervalence Charge Transfer Absorption of the One-Electron Reduced State
The structurally characterized (abpy)PtCl2, abpy = 2,2'-azobispyridine, reveals a strong metal/ligand p interaction as supported by DFT calcns. Unexpectedly, its chem. or electrochem. redn. occurs irreversibly to yield EPR-detectable (μ,η2:η2-abpy)PtCl22.bul.- and, as the main product of chloride dissocn., the structurally identified and DFT-calcd. dinuclear (m,h2:h1-abpy)PtCl22+ with a novel coordination mode for abpy and isolated as tetrachlorozincate. Stepwise reversible 1-electron redn. of that dimer, sepd. by 0.24 V, exhibits an intense near-IR band for the monocationic intermediate (abpy-I)(abpy)Pt2Cl2.bul.+ at 1220 nm (e = 3370 M-1 cm-1) which is attributed to a ligand-to-ligand intervalence charge-transfer transition. on SciFinder(R)
%0 Journal Article
%1 Dogan.2004b
%A Dogan, Akbey
%A Sarkar, Biprajit
%A Klein, Axel
%A Lissner, Falk
%A Schleid, Thomas
%A Fiedler, Jan
%A Zalis, Stanislav
%A Jain, Vimal K.
%A Kaim, Wolfgang.
%D 2004
%J Inorganic Chemistry
%K azobispyridine chloro complex complex;platinum crystal dimer monomer platinum prepn redn structure
%N 19
%P 5973--5980
%R 10.1021/ic049941t
%T Complex Reduction Chemistry of (abpy)PtCl2, abpy = 2,2'-Azobispyridine: Formation of Cyclic (m,h2:h1-abpy)PtCl22+ with a New Coordination Mode for abpy and a Near-Infrared Ligand-to-Ligand Intervalence Charge Transfer Absorption of the One-Electron Reduced State
%V 43
%X The structurally characterized (abpy)PtCl2, abpy = 2,2'-azobispyridine, reveals a strong metal/ligand p interaction as supported by DFT calcns. Unexpectedly, its chem. or electrochem. redn. occurs irreversibly to yield EPR-detectable (μ,η2:η2-abpy)PtCl22.bul.- and, as the main product of chloride dissocn., the structurally identified and DFT-calcd. dinuclear (m,h2:h1-abpy)PtCl22+ with a novel coordination mode for abpy and isolated as tetrachlorozincate. Stepwise reversible 1-electron redn. of that dimer, sepd. by 0.24 V, exhibits an intense near-IR band for the monocationic intermediate (abpy-I)(abpy)Pt2Cl2.bul.+ at 1220 nm (e = 3370 M-1 cm-1) which is attributed to a ligand-to-ligand intervalence charge-transfer transition. on SciFinder(R)
@article{Dogan.2004b,
abstract = {The structurally characterized (abpy)PtCl2, abpy = 2,2'-azobispyridine, reveals a strong metal/ligand \textgreek{p} interaction as supported by DFT calcns. Unexpectedly, its chem. or electrochem. redn. occurs irreversibly to yield EPR-detectable {(μ,η2:η2-abpy)[PtCl2]2}.bul.- and, as the main product of chloride dissocn., the structurally identified and DFT-calcd. dinuclear [(\textgreek{m},\textgreek{h}2:\textgreek{h}1-abpy)PtCl]22+ with a novel coordination mode for abpy and isolated as tetrachlorozincate. Stepwise reversible 1-electron redn. of that dimer, sepd. by 0.24 V, exhibits an intense near-IR band for the monocationic intermediate [(abpy-I)(abpy)Pt2Cl2].bul.+ at 1220 nm (\textgreek{e} = 3370 M-1 cm-1) which is attributed to a ligand-to-ligand intervalence charge-transfer transition. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Dogan, Akbey and Sarkar, Biprajit and Klein, Axel and Lissner, Falk and Schleid, Thomas and Fiedler, Jan and Zalis, Stanislav and Jain, Vimal K. and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2359acfa04dd55f9a348c45dd6016d53c/b_schwederski},
doi = {10.1021/ic049941t},
interhash = {076f1ff2dbb5ba77e6212d8030b4c342},
intrahash = {359acfa04dd55f9a348c45dd6016d53c},
issn = {0020-1669},
journal = {Inorganic Chemistry},
keywords = {azobispyridine chloro complex complex;platinum crystal dimer monomer platinum prepn redn structure},
number = 19,
pages = {5973--5980},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Complex Reduction Chemistry of (abpy)PtCl2, abpy = 2,2'-Azobispyridine: Formation of Cyclic [(\textgreek{m},\textgreek{h}2:\textgreek{h}1-abpy)PtCl]22+ with a New Coordination Mode for abpy and a Near-Infrared Ligand-to-Ligand Intervalence Charge Transfer Absorption of the One-Electron Reduced State},
volume = 43,
year = 2004
}