The reversible redn. of Os(CN)5(NO)2-, the osmium analog of the nitroprusside ion, was studied by spectroelectrochem. techniques (IR, UV-visible, EPR). The strong shift of the nitrosyl stretching band from 1850 to 1560 cm-1 (in acetonitrile) already indicates nitrosyl ligand-centered redn. in comparison to the smaller shifts for the cyanide frequencies (2140 $\rightarrow$ 2080 cm-1). Remarkably, the g factor anal. (g‖ = 2.017, g$\bot$ = 2.003) for electrogenerated Os(CN)5(NO)3- does not reflect any effect from the 5d element osmium with its high spin-orbit coupling const.; only the need to apply helium temps. for EPR signal observation indicates a heavy transition metal. on SciFinder(R)
%0 Journal Article
%1 Baumann.1999b
%A Baumann, Frank
%A Kaim, Wolfgang
%A Baraldo, Luis M.
%A Slep, Leonardo D.
%A Olabe, Jose A.
%A Fiedler, Jan.
%D 1999
%J Inorganica Chimica Acta
%K ESR complex cyano electrochem nitrosyl osmium prepn redn spectroelectrochem
%N 1
%P 129--133
%R 10.1016/S0020-1693(98)00254-0
%T Reduction of the NO+ ligand in the pentacyanonitrosylosmate(II) ion
%V 285
%X The reversible redn. of Os(CN)5(NO)2-, the osmium analog of the nitroprusside ion, was studied by spectroelectrochem. techniques (IR, UV-visible, EPR). The strong shift of the nitrosyl stretching band from 1850 to 1560 cm-1 (in acetonitrile) already indicates nitrosyl ligand-centered redn. in comparison to the smaller shifts for the cyanide frequencies (2140 $\rightarrow$ 2080 cm-1). Remarkably, the g factor anal. (g‖ = 2.017, g$\bot$ = 2.003) for electrogenerated Os(CN)5(NO)3- does not reflect any effect from the 5d element osmium with its high spin-orbit coupling const.; only the need to apply helium temps. for EPR signal observation indicates a heavy transition metal. on SciFinder(R)
@article{Baumann.1999b,
abstract = {The reversible redn. of [Os(CN)5(NO)]2-, the osmium analog of the nitroprusside ion, was studied by spectroelectrochem. techniques (IR, UV-visible, EPR). The strong shift of the nitrosyl stretching band from 1850 to 1560 cm-1 (in acetonitrile) already indicates nitrosyl ligand-centered redn. in comparison to the smaller shifts for the cyanide frequencies (2140 $\rightarrow$ 2080 cm-1). Remarkably, the g factor anal. (g‖ = 2.017, g$\bot$ = 2.003) for electrogenerated [Os(CN)5(NO)]3- does not reflect any effect from the 5d element osmium with its high spin-orbit coupling const.; only the need to apply helium temps. for EPR signal observation indicates a heavy transition metal. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Baumann, Frank and Kaim, Wolfgang and Baraldo, Luis M. and Slep, Leonardo D. and Olabe, Jose A. and Fiedler, Jan.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/27652c91f876d41af7ec16f588a406d09/b_schwederski},
doi = {10.1016/S0020-1693(98)00254-0},
interhash = {65a3dea9aaf311b7c21c3ccadf863fbf},
intrahash = {7652c91f876d41af7ec16f588a406d09},
issn = {0020-1693},
journal = {Inorganica Chimica Acta},
keywords = {ESR complex cyano electrochem nitrosyl osmium prepn redn spectroelectrochem},
number = 1,
pages = {129--133},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Reduction of the NO+ ligand in the pentacyanonitrosylosmate(II) ion},
volume = 285,
year = 1999
}
