Low temperature ultraviolet photolysis of various glasses of the pentacyanonitrosylferrate(II) ion, [Fe(CN)5(NO)]2?
- 1 January 1982
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 10,p. 2041-2045
- https://doi.org/10.1039/dt9820002041
Abstract
Exposure of dilute solutions of [Fe(CN)5(NO)]2– ions to u. v. light at 77 K gave a range of paramagnetic products detected by e.s.r. spectroscopy. In aprotic solvents the major route involved electron transfer from solvent to give [Fe(CN)5(NO)]3–(I′) which, on annealing, gave [Fe(CN)4(NO)]2–(I)+ CN–. Such a route cannot be invoked for aqueous systems and an alternative route involving photoionisation followed by electron capture to give [Fe(CN)5(NO)]3–(II) is suggested. Species (I′) and (I) have their unpaired electrons primarily in the 3dz2 ion orbital whereas for species (II) it is largely localised on the NO ligand. On annealing, species (II) also gave species (I) plus CN–.Keywords
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