Crystal and molecular structure of sodium pentacyanonitrosylruthenate(II) dihydrate and its spectroscopic properties and reactivity

Three Redox States of Metallonitrosyls in Aqueous Solution

“…of [Fe(CN) 5 NO] 2À , a weak oxidant (E ¼ 0.05 V), to the nitroxyl complexes. At pH 6, no spectral changes are apparent; however, at pH 10 the immediate formation of [Fe(CN) 5 NO] 3À is achieved, revealing quantitatively a comproportionation process, reaction (32), preceded by the reverse of reaction (30).…”

Theoretical study on the structure of the ground state and photo-induced metastable states of [M(CN)5NO]2− (M = Ru, Fe), and mechanism of the photo-rearrangement among them

“…Our calculated vertical excitation energies (MRSDCI þ Q) at GS, MS1, and MS2 are shown in Tables 4, 5, and 6, respectively. The observed excitation energies are available for the three metastable states of the Fe complex [6] and only for GS of the Ru complex [22]. Those observed excitation energies and those calculated using the time dependent density functional theory (TD-DFT) [33,35] are included in the tables for comparison.…”

“…Other than Na 2 [Fe(CN) 5 NO] Á 2 H 2 O, the Ru nitrosyl complex, Na 2 [Ru(CN) 5 NO] Á 2 H 2 O, has showed almost same phenomena as the former does [11,[20][21][22];…”

“…The deviations from the GS values in MS1 and MS2 are at most 5% [34]. Basing on these results, we assumed that the geometry parameters of the M(CN) 5 portion were set to the observed GS values throughout our calculations both for the Fe and Ru complex [13,22].…”

The kinetics and mechanism of the substitution reactions of the aquapentacyanoruthenate(II) ion with naphthalene‐substituted ligands in aqueous medium

“…It can also coordinate typically with only one additional incoming or substituting ligand, easily losing a coordinated water molecule and subsequently forming highly stable nitrogen heterocyclic substituted complexes. Such substituted pentacyanoruthenates(II) offered a possibility for developing a systematic work on structure and reactivity [12,13,[16][17][18]. No such substituted pentacyanoruthenate(II) complexes with naphthalenesubstituted ligands are reported in the literature, which were obtained directly through their substitution reactions with aquapentacyanoruthenate(II) unlike the corresponding aquapentacyanoruthenate(II) ion [1][2][3].…”