Interaction between Trinuclear Regium Complexes of Pyrazolate and Anions, a Computational Study

Abstract

The geometry, energy and electron density properties of the 1:1, 1:2 and 1:3 complexes between cyclic (Py-M)3 (M = Au, Ag and Cu) and halide ions (F−, Cl− and Br−) were studied using Møller Plesset (MP2) computational methods. Three different configurations were explored. In two of them, the anions interact with the metal atoms in planar and apical dispositions, while in the last configuration, the anions interact with the CH(4) group of the pyrazole. The energetic results for the 1:2 and 1:3 complexes are a combination of the specific strength of the interaction plus a repulsive component due to the charge:charge coulombic term. However, stable minima structures with dissociation barriers for the anions indicate that those complexes are stable and (Py-M)3 can hold up to three anions simultaneously. A search in the CSD confirmed the presence of (Pyrazole-Cu)3 systems with two anions interacting in apical disposition.

The Physical Chemistry and Chemical Physics (PCCP) Section of the International Journal of Molecular Sciences in Its Publications: The First 300 Thematic Articles in the First 3 Years

“…This direction is represented by 39 articles [ 28 , 35 , 129 , 134 , 136 , 190 , 191 , 192 , 193 , 194 , 195 , 196 , 197 , 198 , 199 , 200 , 201 , 202 , 203 , 204 , 205 , 206 , 207 , 208 , 209 , 210 , 211 , 212 , 213 , 214 , 215 , 216 , 217 , 218 , 219 , 220 , 221 , 222 , 223 ]. Their distribution, according to the above types, is presented in Table 7 .…”

“…In this research, the given reaction between cyclopentadiene and methyl acrylate was computationally investigated in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM] [PF 6 ], as a basis for the validation of the OPLS-VSIL to properly reproduce a reaction medium environment. The articles of group ( c ) include publications [ 28 , 129 , 136 , 193 , 195 , 199 , 200 , 202 , 208 , 209 , 212 , 213 , 215 , 220 ]: in most of them [ 129 , 136 , 195 , 199 , 200 , 202 , 208 , 209 , 212 , 215 ], the objects of quantum chemical calculations were the chelate and macrocyclic coordination compounds of various s -, p -, d -, and f -elements. The most significant of them seems to be publication [ 136 ], devoted to Pu(IV) and Pu(VI) complexes with tridentate (NNN)-donor-atomic ligands, in particular, di(pyridyl-2)amine, 1,3-diamino-2-azapropane, and 2,6-di(pyridyl-2) pyridine, the results of which can be very useful in the development of new extractants and organic sensors of plutonium.…”

Substituent Effects in π‐Hole Regium Bonding Interactions Between Au(p‐X‐Py)2Complexes and Lewis Bases: Anab initioStudy

“…[36] The terms regium bond (RgB) and coinage bond (CiB) have been used indistinctly in the literature to describe noncovalent interactions involving elements belonging group 11 (Cu, Ag and Au). [37,38] Both theoretical and experimental studies have been reported [39][40][41][42][43][44][45][46] that illustrate the ability of group 11 of elements to participate in σ-hole interactions. In addition, the interplay between RgBs and other noncovalent interactions has been also analyzed theoretically.…”

Anion Binding Based on Hg3 Anticrowns as Multidentate Lewis Acidic Hosts

“…Recently, the capture of halide anions by cyclic (Py-M) 3 (M = Cu, Ag, and Au) systems has been computationally studied. 9 Perfluorinated polymercuramacrocycles are a family of compounds with enhanced electrophilicity due to the presence of several Lewis acid centers that can act coordinatively to bind a wide range of anions. Moreover, the presence of the peripheric fluorine atom increases the electron density depletion in the central region of the molecule.…”

“…Among the latter, polymetallic macrocycles make use of simultaneous interactions with multiple metal centers to improve the anion binding capacity. Recently, the capture of halide anions by cyclic (Py-M) 3 (M = Cu, Ag, and Au) systems has been computationally studied …”