Theoretical study of ternary silver fluorides AgMF (M = Cu, Ni, Co) formation at pressures up to 20 GPa.

Only several compounds bearing the Ag(ii) cation and other paramagnetic transition metal cations are known experimentally. Herein, we predict stability and crystal structures of hypothetical ternary silver(ii) fluorides with copper, nickel and cobalt in 1 : 1 stoichiometry at a pressure range from 0 GPa up to 20 GPa employing the evolutionary algorithm in combination with DFT calculations. The calculations show that AgCoF could be synthesized already at ambient conditions but this compound would host diamagnetic Ag(i) and high-spin Co(iii).

The fate of compound with AgF:AgO stoichiometry-A theoretical study.

Metal oxyfluorides constitute a broad group of chemical compounds with a rich spectrum of crystal structures and properties. Surprisingly though, none of the ternary oxyfluorides contains a cation from group 11 of the periodic table. Intending to find one, we focused on the silver derivative, the AgOF system, which may be considered as the 1:1 "adduct" of AgF (i.

Pt as the limit of high oxidation states in oxide-nitride species.

A series of pentaatomic species has been investigated theoretically with relativistic DFT using the M06-L functional with both ZORA scalar relativistic correction, and including spin-orbit coupling effects. The distorted quasi-octahedral local minima for PtNO, PtNO and PtNO corresponding to decavalent Pt were found to be unstable with respect to the elimination of O, NO or N. However, barriers surrounding these minima suggest that these species could be achieved under low-temperature conditions, similar to what was predicted for PtO dications.

The high covalence of metal-ligand bonds as stability limiting factor: the case of Rh(IX)O and Rh(IX)NO.

Rhodium, a 4d transition metal and a lighter analogue of iridium, is known to exhibit its highest VIth oxidation state in RhF molecule. In this report, the stability and decomposition pathways of two species containing rhodium at a potentially formal +IX oxidation state, [RhO] and RhNO, have been investigated theoretically within the framework of the relativistic two-component Hamiltonian calculations. Possible rearrangement into isomers featuring lower formal oxidation numbers has been explored.

Classical and Reverse Substituent Effects in Substituted Anthrol Derivatives.

The substituent effect in 1-, 2-, and 9-anthrols is studied by means of B3LYP/6-311++G(d,p) computation, taking into account substituents (X): NO, CN, OH and NH located in all positions except the adjacent ones. The substituent effect is characterized by approaches based on quantum chemistry: The charge of the substituent active region (cSAR), substituent effect stabilization energy (SESE) and the charge flow index (CFI) describing flow of the charge from X to the fixed group (or vice versa) as well as substituent constants . Changes in properties observed in the fixed group (OH) are described by cSAR(OH).

Toward the Physical Interpretation of Inductive and Resonance Substituent Effects and Reexamination Based on Quantum Chemical Modeling.

An application of a charge of the substituent active region concept to 1-Y,4-X-disubstituted derivatives of bicyclo[2.2.2]octane (BCO) [where Y = NO, COOH, OH, and NH and X = NMe, NH, OH, OMe, Me, H, F, Cl, CF, CN, CHO, COMe, CONH, COOH, NO, and NO] provides a quantitative information on the inductive component of the substituent effect (SE).