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)
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