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Thiocyanate Anions (thiocyanate + anion)
Selected AbstractsChemInform Abstract: Al(HSO4)3/Silica Gel as a Novel Catalytic System for the Ring Opening of Epoxides with Thiocyanate Anion under Solvent-Free Conditions.CHEMINFORM, Issue 26 2010Ali Reza Kiasat Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Ion-Selective Electrodes for Thiocyanate Based on the Dinuclear Zinc(II) Complex of a Bis- N,O -bidentate Schiff BaseELECTROANALYSIS, Issue 12 2004Philippe Bühlmann Abstract An ion selective electrode based on the dinuclear complex formed by two zinc(II) ions and two molecules of the bis- N,O -bidentate Schiff base 2,2,-[methylenebis(4,1-phenylenenitrilomethylidyne)]bisphenol exhibits thiocyanate selectivity with a good discrimination of nitrite, nitrate, and azide. The selectivities of electrode membranes with various compositions indicate that this potentiometric selectivity is based on the formation of a 1,:,1 complex between the thiocyanate anion and the dinuclear ionophore. The 2,:,1 ratio of thiocyanate ions and the dinuclear ionophore that results from higher ratios of cationic sites and ionophore worsens the selectivity, suggesting that binding of a thiocyanate to both zinc(II) centers of the dinuclear ionophore is not favorable. Interestingly, the selectivity patterns of these electrodes differ radically from that of a highly sulfate selective electrode based on a compound reported previously to be the analogous mononuclear 1,:,1 complex of zinc(II) and the same Schiff base. It is suggested that the previously reported 1,:,1 complex with zinc(II) may indeed have been a polymer of the same elemental composition. [source] The Role of Ion Pairs in the Second-Order NLO Response of 4-X-1-Methylpiridinium Salts,CHEMPHYSCHEM, Issue 2 2010Francesca Tessore Dr. Abstract A series of 4-X-1-methylpyridinium cationic nonlinear optical (NLO) chromophores (X=(E)-CHCHC6H5; (E)-CHCHC6H4 -4,-C(CH3)3; (E)-CHCHC6H4 -4,-N(CH3)2; (E)-CHCHC6H4 -4,-N(C4H9)2; (E,E)-(CHCH)2C6H4 -4,-N(CH3)2) with various organic (CF3SO3,, p -CH3C6H4SO3,), inorganic (I,, ClO4,, SCN,, [Hg2I6]2,) and organometallic (cis -[Ir(CO)2I2],) counter anions are studied with the aim of investigating the role of ion pairing and of ionic dissociation or aggregation of ion pairs in controlling their second-order NLO response in anhydrous chloroform solution. The combined use of electronic absorption spectra, conductimetric measurements and pulsed field gradient spin echo (PGSE) NMR experiments show that the second-order NLO response, investigated by the electric-field-induced second harmonic generation (EFISH) technique, of the salts of the cationic NLO chromophores strongly depends upon the nature of the counter anion and concentration. The ion pairs are the major species at concentration around 10,3,M, and their dipole moments were determined. Generally, below 5×10,4,M, ion pairs start to dissociate into ions with parallel increase of the second-order NLO response, due to the increased concentration of purely cationic NLO chromophores with improved NLO response. At concentration higher than 10,3,M, some multipolar aggregates, probably of H type, are formed, with parallel slight decrease of the second-order NLO response. Ion pairing is dependent upon the nature of the counter anion and on the electronic structure of the cationic NLO chromophore. It is very strong for the thiocyanate anion in particular and, albeit to a lesser extent, for the sulfonated anions. The latter show increased tendency to self-aggregate. [source] Redox Modification of EMACs Through the Tuning of Ligands: Heptametal(II) Complexes of Pyrazine-Modulated Oligo-,-pyridylamido LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2009Rayyat Huseyn Ismayilov Abstract Using pyrazine-modulated oligo-,-pyridylamido ligands N2 -(pyrazin-2-yl)- N6 -[6-(pyrazin-2-ylamino)pyridin-2-yl]pyridine-2,6-diamine (H3pzpz) and N2 -(pyrazin-2-yl)- N6 -[6-(pyridin-2-ylamino)pyridin-2-yl]pyridine-2,6-diamine (H3tpz), linear heptametal(II) extended metal atom chains (EMACs) [M7(,7 -L)4X2] [L = pzpz3,, M = NiII, X = Cl, (1), NCS, (2); M = CrII, X = Cl, (3), NCS, (4); L = tpz3,, M = CrII, X = Cl, (5), NCS, (6)] were synthesized and structurally characterized. Electrochemical studies showed that heptanickel(II) complexes can undergo one reversible oxidation at +0.46 V for 1 and +0.52 V for 2. Chromium(II) species 3 exhibited two reversible, one-electron oxidation peaks at +0.61 and +0.88 V, and 5 exhibited three reversible, one-electron oxidation peaks at +0.40, +0.68 and +1.07 V. The redox peaks shifted positively when axial ligands changed from chloride to thiocyanate anions, at +0.67 and +0.92 V for 4 and +0.44, +0.73 and +1.11 V for 6. The introduction of electron-withdrawing pyrazine rings to the spacer ligand retarded oxidation of the heptametal EMACs and stabilized the complexes. In nickel(II) species 1 and 2, both terminal nickel atoms exist in spin state S = 1 whereas all the inner nickel atoms exist in spin state S = 0. Temperature-dependent magnetic research revealed an antiferromagnetic interaction between the two terminal atoms through a superexchange pathway along metal cores with a parameter of about,4 cm,1. Chromium(II) species 3,6 showed a localized structure consisting of three quadruple Cr,Cr bonds and a single terminal CrII atom. Magnetic study revealed a quintet ground state resulting from the isolated, high-spin CrII atom.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Concomitant polymorphic behavior of di-,-thiocyanato-,2N:S;,2S:N -bis[bis(tri- p -fluorophenylphosphine-,P)silver(I)]ACTA CRYSTALLOGRAPHICA SECTION B, Issue 1 2010Bernard Omondi The structures of two polymorphs, both monoclinic P21/n [polymorph (I)] and P21/c [polymorph (II)], of di-,-thiocyanato-,2N:S;,2S:N -bis[bis(tri- p -fluorophenylphosphine-,P)silver(I)] complexes have been determined at 100,K. In both polymorphs the complex has a dinuclear structure where the silver(I) coordinates to two phosphine ligands and two bridging thiocyanate anions to form complexes with distorted tetrahedral geometry. Polymorph (I) has just one half of the [Ag2(SCN)2{P(4-FC6H4)3}4] molecule at (0, ½, 0) from the origin in the asymmetric unit. Polymorph (II) has one and a half molecules of [Ag2(SCN)2{P(4-FC6H4)3}4] in the asymmetric unit; the half molecule is situated at (0, 1, ½), while the full molecule is located at (1/3, ½, 1/3) from the origin. The Ag,P bond distances range from 2.4437,(4) to 2.4956,(7),Å in both polymorphs. The Ag,S distances are 2.5773,(7),Å in (I) and 2.5457,(5), 2.5576,(5) and 2.5576,(5),Å in (II). The full molecule in polymorph (II) has slightly shorter Ag,N bond distances [2.375,(1) and 2.367,(2),Å] compared with the half molecules in both polymorphs [2.409,(2),Å in (II) and 2.395,(2),Å in (I)]. The two polymorphs are compared using r.m.s. overlay calculations as well as half-normal probability plot analysis. [source] Two novel silver(I) coordination polymers: poly[(,2 -2-aminopyrimidine-,2N1:N3)bis(,3 -thiocyanato-,3S:S:S)disilver(I)] and poly[(2-amino-4,6-dimethylpyrimidine-,N)(,3 -thiocyanato-,3N:S:S)silver(I)]ACTA CRYSTALLOGRAPHICA SECTION C, Issue 10 2009Geng-Geng Luo 2-Aminopyrimidine (L1) and 2-amino-4,6-dimethylpyrimidine (L2) have been used to create the two novel title complexes, [Ag2(NCS)2(C4H5N3)]n, (I), and [Ag(NCS)(C6H9N3)]n, (II). The structures of complexes (I) and (II) are mainly directed by the steric properties of the ligands. In (I), the L1 ligand is bisected by a twofold rotation axis running through the amine N atom and opposite C atoms of the pyrimidine ring. The thiocyanate anion adopts the rare ,3 -,3S coordination mode to link three tetrahedrally coordinated AgI ions into a two-dimensional honeycomb-like 63 net. The L1 ligands further extend the two-dimensional sheet to form a three-dimensional framework by bridging AgI ions in adjacent layers. In (II), with three formula units in the asymmetric unit, the L2 ligand bonds to a single AgI ion in a monodentate fashion, while the thiocyanate anions adopt a ,3 -,1N,,2S coordination mode to link the AgL2 subunits to form two-dimensional sheets. These layers are linked by N,H...N hydrogen bonds between the noncoordinated amino H atoms and both thiocyanate and pyrimidine N atoms. [source] New Metal-Organic Frameworks with Large Cavities: Selective Sorption and Desorption of Solvent MoleculesCHEMISTRY - A EUROPEAN JOURNAL, Issue 26 2007Yan Wang Abstract Five novel transition metal complexes [CdII3(tpba-2)2(SCN)6],6,THF,3,H2O (1), [CuII3(tpba-2)2(SCN)6],6,THF,3,H2O (2), [NiII3(tpba-2)2(SCN)6],6,THF,3,H2O (3), [CdII2(tpba-2)(SCN)3]ClO4 (4), [CuI3(SCN)6(H3tpba-2)] (5) [TPBA-2 = N,,N,,,N,,, -tris(pyrid-2-ylmethyl)-1,3,5-benzenetricarboxamide, THF=tetrahydrofuran] were obtained by reactions of the corresponding transition metal salts with TPBA-2 ligand in the presence of NH4SCN using layering or solvothermal method, respectively. The results of X-ray crystallographic analysis showed that complexes 1, 2 and 3 are isostructural and have the same 2D honeycomb network structure with Kagomé lattice, in which all the MII (M = Cd, Cu, Ni) atoms are six-coordinated, and the TPBA-2 ligands adopt cis,cis,cis conformation while the thiocyanate anions act as terminal ligands. Capsule-like motifs are found in 1, 2 and 3, in which six THF molecules are hosted, and the results of XPRD and solid-state 13C,NMR spectral measurements showed that the compound 1 can selectively desorb and adsorb THF molecules occurring along with the re-establishment of its crystallinity. In contrast to 1, 2 and 3, complex 4 has different 2D network structure, resulting from TPBA-2 ligands with cis,trans,trans conformation, thiocyanate anions serving as end-to-end bridging ligands, and the incomplete replacement of perchlorate anions, which further link the 2D layers into 3D framework by the hydrogen bonds. In complex 5, the CuII atoms are reduced to CuI during the process of solvothermal reaction, and the CuI atoms are connected by thiocyanate anions to form a 3D porous framework, in which the protonated TPBA-2 ligands are hosted in the cavities as templates. [source] | ||||||||||