Density functional study of electronic, magnetic and hyperfine properties of [M(CN)5NO]2− (M=Fe, Ru) and reduction products

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

“…It has been shown that MS2 and MS1 lie above GS by 1.0 eV and 1.1 eV [11] in the Fe complex and relative stability between the two metastable states is in accord with experimental results by our calculation [34] as well as DFT calculations [30][31][32][33]. Similar results are given for the Ru complex [35][36][37] (see Table 2). Reflecting higher covalency in the second period transition metal than the first period transition metal, the barrier height of the Ru complex is enhanced in comparison with the Fe complex.…”

“…Since stronger stability of the metastable states of Na 2 [Ru(CN) 5 [35,36] and the present authors [37] have performed ab initio CASSCF and MRSDCI calculations.…”

EPR Insensitivity of the Metal‐Nitrosyl Spin‐Bearing Moiety in Complexes [LnRuII‐NO·]k

“…[34] to the Ru II compounds summarized here. In comparison to the results given here, some other calculations [26,29] 3Ϫ displays a g component splitting approaching the axial limit, with g Ќ Ͼ g || . The average value of g is smallest for this species whereas it is slightly larger (in 0.012) for [(cyclam)ClRu(NO)]…”

On the Mechanism of the Thermal Retro‐Cycloaddition of Fulleropyrrolidines (Retro‐Prato Reaction)

“…DFT calculations on [Fe(CN) 5 (NO)] 2− have provided an orbital diagram with a LUMO that is doubly degenerate and predominantly π$\rm{^{{\ast}}_{NO}}$ in character. One‐electron reduction will give an NO‐centred orbital as the new HOMO 57. By way of analogy and short of a rigorous theoretical description of the bonding in 4 (which is given below), this situation would lead one to expect a rhombic g tensor with 14 NO hyperfine splitting for the ESR spectrum of 4 ,29 and this is what we observe.…”