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• W2041058474 abstract "The usual synthetic route to acidoamminechromium(Ill) ions is replacement of H2O ligands by anionic groups [1]. So far, cyanoammine complexes have not been reported; a possible reason is that cyanide cannot be bound to chromium by such a procedure, as deprotonation of coordinated water by this strongly basic anion prevents substitution in both aqueous and nonaqueous media. An alternative reaction was therefore sought to obtain the previously unknown trans- andcis-Cr(NH3)4(CN)+2 species, particularly in order to investigate their excited-state reactions. The photochemical interest arises from the extreme spectrochemical position and the π-acceptor bonding of the CN− ligand. The method is one of CN− anation ofCr(NH3)4(DMSO)3+2 compounds (DMSO = dimethylsulfoxide), and this report concerns the role of the solvent in determining the stereochemistry of the products. Due to the absence of acidic hydrogens, substitution of DMSO takes place smoothly either in water or in DMSO as solvent. The general pattern of reactivity is summarized in the following Scheme (where N = NH3): The product yield is larger in the dipolar aprotic solvent than in water, because of various factors: (a) the enhancement of ion association [2]; (b) a poorer anion solvation [3]; (c) the absence of any hydrolysis. Reaction of either trans- orcis-Cr(NH3)4(DMSO)3+2 in DMSO leads to an identical mixture of trans- and cis-Cr(NH3)4(CN)+2 cations, as the presence of CN− induces fast and complete trans → cis isomerization, prior to anation. Stereomobility of chromium(III) species is possible in this solvent [4] and ion pairing with the entering anion may drive the equilibrium mixture towards the polar cis form. An unexpected finding is that partial cis → trans isomerization (the direction is rather uncommon for Cr(III)) accompanies successive entry of CN−. In this stage, the decreased (1+) complex charge should disfavor ion pairing stabilization with respect to mutual repulsion of the coordinated CN− groups. Exactly the same result is achieved starting from either trans- or cis- Cr(NH3)4(DMSO)CI2→. Although less efficient, anation in H20 occurs with retention of configuration, as is generally observed for chromium(lIl) substitutions in aqueous solution [1, 5]. In either case relatively fast subsequentcoordination of more CN− subtracts part of t001. Ligand-Field Absorption Maxima of the Cr(NH3)4(CN)+2 Ions In Water.Transitiontrans IsomerCis isomerλ, nm (ϵ)λ, nm (ϵ)4B1 → 4B2, 4E(4T2g)440(42.6)436(49.0)4B1 → 4E, 4A2(4T1g)344(41.5)342(37.2) the product, to yield the neutral Cr(NH3)3(CN)3 species. t001. Ligand-Field Absorption Maxima of the Cr(NH3)4(CN)+2 Ions In Water. Both dicyanotetraammine complexes were isolated and characterized by elemental analysis. Their 1+ charge was confirmed by electrical conductance and ion-exchange tests. The IR spectrum exhibits the stretching frequency of coordinated cyanide at 2130 cm−1. The ligand-field absorption maxima, reported in Table I, agree with theoretical predictions [6]. Even though the electronic spectra of the individual isomers are not sufficiently diagnostic of the configurations, definite stereochemical evidence is provided by the respective products of acid hydrolysis, trans- and cis-Cr(NH3)4(H20)3+2,which are formed with complete stereoretention and present significantly different absorption features." @default.
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• W2041058474 date "1980-01-01" @default.
• W2041058474 modified "2023-09-23" @default.
• W2041058474 title "Solvent dependent stereochemistry of cyanide anation of some chromium(III) complexes" @default.
• W2041058474 cites W2001807124 @default.
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• W2041058474 doi "https://doi.org/10.1016/s0020-1693(00)92233-3" @default.
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