The diorganoplatinum(II) complexes (bpy)Pt(Ph)2, (bpym)Pt(Ph)2, (m-bpym)(Pt(p-tol)2)2, and (m-bpym)(PtAd2)2, (bpy = 2,2'-bipyridine; bpym = 2,2'=bipyrimidine; Ph = phenyl; p-tol = p-tolyl; Ad = (1-adamantylmethyl) were subjected to two successive one-electron redns., and the one-electron redn. products were studied in situ by UV-vis-near-IR and EPR spectroscopy. The first redn. is at the heterocyclic ligand, in contrast to the metal-centered redns. in such closely similar species as Pt(bpy)(py)22+. We attribute this difference to the greater ligand field strength of carbanionic as opposed to neutral N-bound ligands. While the EPR signals of the paramagnetic species show sizable g anisotropy (1.92-2.02) in frozen soln. due to the large spin-orbit coupling const. of the metal, the rhombic g pattern, the low isotropic values (giso \textless 2), and the isotropic hyperfine coupling as obsd. and reproduced in the case of (bpym)Pt(Ph)2.bul.- all suggest a predominant localization of the unpaired electron at the a-diimine ligand. on SciFinder(R)
%0 Journal Article
%1 Braterman.1992c
%A Braterman, Paul S.
%A Song, Jae Inh
%A Vogler, Conny
%A Kaim, Wolfgang.
%D 1992
%J Inorganic Chemistry
%K EPR complex diimine heterocyclic platinum reduced
%N 2
%P 222--224
%R 10.1021/ic00028a018
%T EPR and absorption spectra of singly reduced mono- and dinuclear diorganoplatinum complexes of heterocyclic a-diimines
%V 31
%X The diorganoplatinum(II) complexes (bpy)Pt(Ph)2, (bpym)Pt(Ph)2, (m-bpym)(Pt(p-tol)2)2, and (m-bpym)(PtAd2)2, (bpy = 2,2'-bipyridine; bpym = 2,2'=bipyrimidine; Ph = phenyl; p-tol = p-tolyl; Ad = (1-adamantylmethyl) were subjected to two successive one-electron redns., and the one-electron redn. products were studied in situ by UV-vis-near-IR and EPR spectroscopy. The first redn. is at the heterocyclic ligand, in contrast to the metal-centered redns. in such closely similar species as Pt(bpy)(py)22+. We attribute this difference to the greater ligand field strength of carbanionic as opposed to neutral N-bound ligands. While the EPR signals of the paramagnetic species show sizable g anisotropy (1.92-2.02) in frozen soln. due to the large spin-orbit coupling const. of the metal, the rhombic g pattern, the low isotropic values (giso \textless 2), and the isotropic hyperfine coupling as obsd. and reproduced in the case of (bpym)Pt(Ph)2.bul.- all suggest a predominant localization of the unpaired electron at the a-diimine ligand. on SciFinder(R)
@article{Braterman.1992c,
abstract = {The diorganoplatinum(II) complexes [(bpy)Pt(Ph)2], [(bpym)Pt(Ph)2], [(\textgreek{m}-bpym)(Pt(p-tol)2)2], and [(\textgreek{m}-bpym)(PtAd2)2], (bpy = 2,2'-bipyridine; bpym = 2,2'=bipyrimidine; Ph = phenyl; p-tol = p-tolyl; Ad = (1-adamantylmethyl) were subjected to two successive one-electron redns., and the one-electron redn. products were studied in situ by UV-vis-near-IR and EPR spectroscopy. The first redn. is at the heterocyclic ligand, in contrast to the metal-centered redns. in such closely similar species as [Pt(bpy)(py)2]2+. We attribute this difference to the greater ligand field strength of carbanionic as opposed to neutral N-bound ligands. While the EPR signals of the paramagnetic species show sizable g anisotropy (1.92-2.02) in frozen soln. due to the large spin-orbit coupling const. of the metal, the rhombic g pattern, the low isotropic values (giso {\textless} 2), and the isotropic hyperfine coupling as obsd. and reproduced in the case of [(bpym)Pt(Ph)2].bul.- all suggest a predominant localization of the unpaired electron at the \textgreek{a}-diimine ligand. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Braterman, Paul S. and Song, Jae Inh and Vogler, Conny and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2c140679ef9adc3759719635769185354/huebleriac},
doi = {10.1021/ic00028a018},
interhash = {89016c9a443b16ac56f9679d23eb44c4},
intrahash = {c140679ef9adc3759719635769185354},
issn = {0020-1669},
journal = {Inorganic Chemistry},
keywords = {EPR complex diimine heterocyclic platinum reduced},
number = 2,
pages = {222--224},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {EPR and absorption spectra of singly reduced mono- and dinuclear diorganoplatinum complexes of heterocyclic \textgreek{a}-diimines},
volume = 31,
year = 1992
}