Reduction Of The No+ Ligand In The Pentacyanonitrosylosmate(Ii) Ion

BAUMANN, F.; KAIM, W.; BARALDO, L. M.; SLEP, L. D.; OLABE, J. A.; FIEDLER, J.

INORGANICA CHIMICA ACTA

Elsevier

Año: 1999 vol. 285 p. 129 - 133

0020-1693

The reversible reduction of [Os(CN)(5)(NO)](2-) the osmium analog of the nitroprusside ion, has been studied by sprctroelectrochemical techniques (IR, UV-Vis, EPR). The strong shift of the nitrosyl stretching band from 1850 to 1560 cm(-1) (in acetonitrile) already indicates nitrosyl ligand-centered reduction in comparison to the smaller shifts for the cyanide frequencies (2140 --> 2080 cm(-1)). Remarkably, the g factor analysis (g(parallel to) = 2.017, g(perpendicular to) = 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 constant; only the need to apply helium temperatures for EPR signal observation indicates the presence of a heavy transition metal