Ligand‐Exchange Processes on Solvated Lithium Cations: Acetonitrile and Hydrogen Cyanide

Ligand Exchange Processes on Solvated Zinc Cations – DFT Analysis of Hydrogen Cyanide Exchange on [Zn(HCN)6]2+

“…In accordance with the expected trend, the calculated change in the Zn-N bond lengths during the exchange reaction (∆∑) were found to be positive for the limiting dissociative mechanism and negative for the associative interchange mechanism (see Table 1). In addition, ∑r 3 increases significantly on going from the transition state, The overall mechanistic findings demonstrate that as in the case of Li + , [17,18] Be 2+ , [19] and Al…”

“…Following the suggestions of Hartmann et al, [13] and for comparison with recent studies on solvent exchange at Li + , [17,18,22] Be 2+ , [19,23] and Al 3+ , [20,21] we fully optimized the structures at the B3LYP/6-311+G** level of theory [24] and characterized by computation of vibration frequencies the structures as local minima or transition states.…”

On the nature of tetraalkylammonium ions in common electrochemical solvents: General and specific solvation – Quantitative aspects

“…The complexes with MeOH and AN should be even more labile. In fact, this has been found to be so experimentally: NMR experiments have established the fact that lithium ion coordinates strongly to four acetonitrile molecules yet they rapidly exchange with solvent in acetonitrile [13]. Similar behavior is found with inorganic complexes in nucleophilic solvents; e.g., addition of DMSO to a solution of Nd(ClO 4 ) 3 in AN results in formation of an equilibrium mixture of nona-and decasolvates Nd +3 /(DMSO) n in which the apparent value of n is 9.7 [53].…”

“…For example, X-ray crystallographic analyses of lithium compounds crystallized from tetrahydrofuran (THF) show the presence of four THF molecules tetrahedrally distributed around lithium, with the oxygen atom of each THF molecule directed toward the central lithium ion [8][9][10]. Lithium ion has also been found to be specifically solvated by four acetone [11], dimethylsulfoxide [12], and acetonitrile [13] molecules. Furthermore, specific solvation is not necessarily restricted to metal ions.…”

Application of High Pressure in the Elucidation of Inorganic and Bioinorganic Reaction Mechanisms

“…Again a computational study (DFT method) was employed to probe the mechanism of solvent exchange for both CH 3 CN and HCN. 387 Exchange proceeds by a limiting associative mechanism involving the formation of relatively stable fivecoordinate intermediate species.…”