Reply

Abstract

Trust in experiments: As DFT calculations suggest that the hydrogen bonding of water molecules can stabilize a seven‐coordinate ruthenium–oxo complex to exhibit a singlet spin state, experiments have shown that the novel seven‐coordinate pentaganol‐bipyramidal ruthenium–oxo complex has a singlet ground state. Nevertheless, it displays the same reactivity as an analogous triplet‐state complex.

Spectral signature of a Ru(ii, iii, iv) complex: a combined experimental and theoretical investigation

“…Several examples of six-coordinated Ru(IV) complexes displaying either a diamagnetic or a paramagnetic ground state exist in the literature. [27][28][29][30][31] The recent theoretical paper of Gonzalez and collaborators shows how DFT is indeed able to provide a realistic picture of the spin state ordering in the case of Ru(IV) compounds. 27 species the second oxidation involves, to a slightly larger extent than in the case of the Ru(IV) S=1 , also the ligands (and in particular the acac-TIPSA moiety) which may explain the difference in structure computed for the Ru(IV) S=1 and Ru(IV) S=0 complexes.…”

“…[25][26] Remarkably, theoretical works concerning Ru(III) and Ru(IV) complexes are less numerous than those devoted to Ru(II) complexes and mainly related to the investigation of catalytically active compounds (both of synthetic or biomimetic relevance). [27][28][29][30][31] The paper is structured as follows: after a brief description of the computational approaches used…”

“…25,26 Remarkably, theoretical works concerning Ru(III) and Ru(IV) complexes are less numerous than those devoted to Ru(II) complexes and mainly related to the investigation of catalytically active compounds (both of synthetic or biomimetic relevance). [27][28][29][30][31] The paper is structured as follows: after a brief description of the computational approaches used (section 2), the electronic and geometrical features are discussed in section 3.1 together with the absorption properties of each compound (section 3.2). Finally, some general conclusions, concerning the accuracy of the methods and the spectroscopic signature of the Ru centers, are drawn in the last section.…”

“…The localization of the hole(s) on the Ru atom for the Ru(III) complex after its oxidation from the Ru(II) d 6 closed shell electronic configuration, is confirmed by the computed Mulliken Atomic Spin Density (0.84 e-) actually corresponding to the presence of an unpaired electron on the Ru atom.Analogously the oxidation from Ru(III) to Ru(IV) seems mainly to take place on the Ru center, the spin density computed on this latter being, for the Ru(IV) S=1 complex, of 1.25 e-.Oxidation of the Ru(III) species yields to the Ru(IV) species for which the intermediate spin triplet state (S=1) is indeed computed to be more stable than the corresponding singlet state of roughly 10 kcal/mol. Several examples of six-coordinated Ru(IV) complexes displaying either a diamagnetic or a paramagnetic ground state exist in literature [27][28][29][30][31]. The recent theoretical paper of Gonzalez and collaborators shows how DFT is indeed able to provide a realistic picture of the spin state ordering in the case of Ru(IV) compounds 27.…”

Structure and spin state of nonheme FeIVO complexes depending on temperature: predictive insights from DFT calculations and experiments

“…One is therefore limited to measure the spin states at the reactant or product states. Despite attempts to address this question by such studies, 12 this provided limited information regarding this issue, and especially so about the timing of spin change ( i.e. , before or after the TS).…”