540-72-7Relevant articles and documents
COMPOUNDS CONTAINING HYDRIDO-TRICYANO-BORATE ANIONS
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Page/Page column 52, (2013/02/28)
The present invention relates to compounds containing hydrido-tricya-borate anions, their preparation and their use, in particular as part of electrolyte formulations for electrochemical or optoelectronic devices.
Kinetic study of an autocatalytic reaction: Nitrosation of formamidine disulfide
Francisco, Vitor,Garcia-Rio, Luis,Antonio Moreira, Jose,Stedman, Geoffrey
body text, p. 2292 - 2298 (2009/03/11)
The reaction kinetics for the acid nitrosation of formamidine disulfide (FDS) show an autocatalytic behavior that arises from the fact that the thiocyanate ion formed as a product acts as a powerful catalyst for the nitrosation reaction. In the presence of added nucleophiles the suppression of the autocatalytic route results from competition for the nitrous acid between the added halides and the thiocyanate anion, which is formed as a reaction product. Analysis of the kinetic data enabled extraction of the bimolecular rate constants, kNO+ = (3.2 ± 1.8) × 1010 M -1 s-1; kNOSCN = (2.1 ± 0.2) × 105 M-1 s-1; kNOBr = (9.4 ± 0.2) × 106 M-1 s1 and kNOCl = (4.0 ± 0.2) × 107 M-1 s-1, for the pathways catalyzed by SCN-, Br- and Cl-, respectively. Kinetic results are consistent with the attack on the nitrosating agent as the rate limiting step, i.e., the nitrosation of FDS behaves in a similar manner to the nitrosation of an amine. Rather different behavior is found for other substrates with an imino moiety adjacent to an amino nitrogen, such as the guanidines, which react by a mechanism in which the rate limiting step is the reorganization of the nitrosated substrate. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008.
Recovery of sodium thiocynate from industrial process solution using nanofiltration technique
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Page/Page column 6-11, (2008/06/13)
The present invention relates to a membrane-based nanofiltration process for separating sodium thiocyanate (NaSCN) from industrial solution containing impurities such as β-sulfopropionic acid, β-sulfopropionitrile, sodium sulfate and salts of iron and calcium in a single step to obtain a colorless aqueous solution for spinning of acrylic fibre in textile industry.
Vanadium nitride functionalization and denitrogenation by carbon disulfide and dioxide
Brask, Justin K.,Dura-Vila, Victor,Diaconescu, Paula L.,Cummins, Christopher C.
, p. 902 - 903 (2007/10/03)
A dramatic difference in behavior is observed for the dithiocarbamate and carbamate complexes [Ar(Butt)N]3V(NCE2)Na(THF)2(E = S or O, respectively), prepared from the corresponding nitride species {[Ar(Butt)N]3V≡NNa}2 by way of a nucleophilic addition reaction involving carbon disulfide or dioxide, and is rationalized with the aid of DFT calculations.
Complexation of phosphoryl-containing mono-, bi- and tri-podands with alkali cations in acetonitrile. Structure of the complexes and binding selectivity
Solov'ev, Vitaly P.,Baulin, Vladimir E.,Strakhova, Nadezhda N.,Kazachenko, Vladimir P.,Belsky, Vitaly K.,Varnek, Alexandre A.,Volkova, Tatiana A.,Wipff, Georges
, p. 1489 - 1498 (2007/10/03)
We present experimental and theoretical studies on new ionophores (L) which possess a high complexation ability for Li+or Na+cations. Four tri-podands(R1-O-C2H4-)3N[R 1 = -CH2-P(O)Ph2(P1), -C2H4-P(O)Ph2 (P2), -o-C6H4P(O)Ph2 (P3) and -o-C6H4-CH2-P(O)Ph2 (P4)], one bi-podand (R2-O-C2H4-)2N-CH3 [R2 = -o-C6H4-CH2-P(O)Ph2 (P5)] and one mono-podand [R2-O-(CH2-CH2-O)3R2 (P6)] containing phosphine oxide terminal groups have been synthesised. Stability constants, enthalpies and entropies of their complexation with lithium, sodium and potassium thiocyanates have been determined in acetonitrile at 298 K by a calorimetric titration technique. We find that tri-podands form a variety of complexes [(M+)3L, (M+)2L, M+L and M+L2)], whereas the bi- and mono-podand form only M+L complexes with Li+ and Na+, and M+L and M+L2 complexes with K+. Formation of poly-nuclear (M+)nL complexes of tri-podands in solution has been confirmed by electro-spray mass spectrometry. At relatively small concentrations of the ligand (CL0)S P1 binds Na+ much better than Li+, whereas P4 and P5 display a remarkable Li+/Na+ selectivity; at large CL0 the complexation selectivity decreases. X-Ray diffraction studies performed on monocrystals of complexes of NaNCS with tri-podands P2 and P3 show that Na+ is encapsulated inside a 'basket-like' pseudocavity, coordinating all donor atoms of the tri-podand. Molecular dynamics simulations on P2, P3 and P4 and on their 1:1 complexes with M+ in acetonitrile solution suggest that the structures of M+L complexes in solution are similar to those found for P2 and P3 complexes in the solid state.
Kinetics and Mechanism of the Reaction between Tetrachloro- and Tetrabromo-aurate(III) and Thiocyanate
Elding, Lars I.,Groening, Ann-B.,Groening, Oesten
, p. 1093 - 1100 (2007/10/02)
The kinetics and mechanism for the overall reaction (i) (X=Cl or Br) have been studied at 25.0 deg C using stopped-flow spectrophotometry. 3- + 7SCN- + 4H2O -> 3- + HSO4- + HCN + 12X- + 6H+ (i) The reaction takes place in two kinetically well separated steps.The initial, rapid process can be identified as stepwise ligand substitutions (ii) (n=0-3) which take place via direct ligand displacements, the solvent path being negligible. 4-n(SCN)n>- + SCN-3-n(SCN)n+1>- + X- (ii) The substitution kinetics give no evidence for formation of persistent five-co-ordinate intermediates.The subsequent slower reaction is due to reduction of gold(III) to gold(I) thiocyanato-species.The rate of this step varies by four orders of magnitude within the accessible concentration interval of gold (1E-6-1E-2 mol dm-3).At high gold concentrations the reduction is slow and follows no simple-order kinetics due to inhibition by the cyanide formed as a product.This inhibition is eliminated for gold concentrations less than 5E-6 mol dm-3, where the redox reaction is rapid and strictly first order with respect to the concentrations of thiocyanate and gold complex.The mechanism for the reductive elimination is intermolecular involving a reaction between the gold(III) complex and an outer-sphere thiocyanate.Rate constants for reduction of - and - by thiocyanate at 25 deg C are (5+/-2)E4 and (2.4+/-0.2)E3 dm3 mol-1 s-1 respectively, for a 1.00 mol dm-3 perchlorate medium.
