Solid-phase ligand substitution processes by outer-sphere anions in isomeric mixed-ligand hexamine chromium(III) complexes

1985 ◽  
Vol 30 (2) ◽  
pp. 365-375 ◽  
Author(s):  
Yu. H. Shevchenko ◽  
V. A. Logvinenko ◽  
N. I. Yashchina ◽  
E. A. Pisarev ◽  
G. V. Gavrilova
Keyword(s):  
Solid Phase ◽  
Outer Sphere ◽  
Ligand Substitution ◽  
Mixed Ligand

Outer-sphere interaction of (S)-asparagine and (S)-glutamine with [Co(NH3)6]3+ ion and its possible role in ligand substitution

1987 ◽  
Vol 52 (10) ◽  
pp. 2457-2459
Author(s):  
František Jursík
Keyword(s):  
Amino Acids ◽  
Transition Region ◽  
Alkaline Medium ◽  
Optical Activity ◽  
Substitution Reaction ◽  
Outer Sphere ◽  
Ligand Substitution ◽  
Cotton Effect ◽  
Negative Cotton Effect

Optical activity of the achiral cation [Co(NH3)6]3+ is induced both by (S)-AsnONa and (S)-GlnONa, as shown by a negative Cotton effect in the 1A1g → 1T1g transition region. An outer-sphere interaction by three-point attachment of the amides can explain the fact that substitution reaction of [Co(NH3)6]3+ with the mentioned amides in an alkaline medium is unusually slow as compared with other amino acids.

scholarly journals Binding of Gold(III) from Solutions by the [Ag6{S2CN(CH2)6}6] Cluster: Synthesis, Thermal Behavior, and Self-Organization of the Supramolecular Structure of the Double Complex [Au{S2CN(CH2)6}2]2[AgCl2]Cl·2CHCl3 (Role of Secondary Au⋅⋅⋅Cl, Ag⋅⋅⋅S, and Cl⋅⋅⋅Cl Interactions)

2021 ◽  
Vol 47 (11) ◽  
pp. 769-779
Author(s):  
E. V. Korneeva ◽  
E. V. Novikova ◽  
O. V. Loseva ◽  
A. I. Smolentsev ◽  
A. V. Ivanov
Keyword(s):  
Thermal Behavior ◽  
Supramolecular Structure ◽  
Solid Phase ◽  
Simultaneous Thermal Analysis ◽  
Outer Sphere ◽  
Chloride Ions ◽  
Double Complex ◽  
Coordination Spheres ◽  
High Level ◽  
Oppositely Charged

Abstract The capability of silver(I) cyclo-hexamethylenedithiocarbamate to concentrate gold(III) from solutions characterized by a high level of salinity (5.15 M NaCl) into the solid phase has been established. The double chloroform-solvated Au(III)–Ag(I) complex [Au{S2CN(CH2)6}2]2[AgCl2]Cl·2CHCl3 (I) was preparatively isolated as an individual form of binding of [AuCl4]– anions. The composition of the ionic structural units of compound I indicates that gold(III) binding from a solution to the solid phase is accompanied by the complete redistribution of the HmDtc ligands between the coordination spheres of Ag(I) and Au(III). Complex I characterized by IR spectroscopy, simultaneous thermal analysis, and X-ray structure analysis (CIF file CCDC no. 2051654) exhibits the supramolecular structure containing two oppositely charged pseudo-polymeric subsystems. Complex cations [Au{S2CN(CH2)6}2]+ and anions [AgCl2]– (in a ratio of 2 : 1) form a complicatedly organized cation-anionic pseudo-polymeric ribbon ({[Au(HmDtc)2]⋅⋅⋅[AgCl2]⋅⋅⋅[Au(HmDtc)2]}+)n due to secondary interactions Ag⋅⋅⋅S (3.2613 Å) and Au⋅⋅⋅Cl (3.2765 Å). The pseudo-polymeric ribbon consists of two rows of cations and a row of anions. The outer-sphere chloride ions combine the solvate chloroform molecules by two equivalent hydrogen bonds Cl⋅⋅⋅H–C yielding anion-molecular triads [Cl3CH⋅⋅⋅Cl⋅⋅⋅HCCl3]–, which are involved in the formation of the supramolecular ribbon due to the secondary Cl⋅⋅⋅Cl interactions (3.4058 Å) between the nonequivalent chlorine atoms of the nearest solvate molecules. The study of the thermal behavior of complex I makes it possible to determine the character of thermolysis and conditions for the quantitative regeneration of bound gold.

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