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1.
The kinetics and mechanism of the adduct formation of diorganotin(IV)dichlorides with Co(II) tetraaza Schiff base complexes, such as [Co(ampen)] {[N,N′‐ethylenebis‐(o‐amino‐α‐phenylbenzylideneiminato)cobalt(II)]}, [Co(campen)] {[N,N′‐ethylenebis‐(5‐chloro‐o‐amino‐α‐phenylbenzylideneiminato)cobalt(II)]}, and [Co(amaen)] {[N,N′‐ethylenebis‐(o‐amino‐α‐methylbenzylideneiminato)cobalt(II)]}, were studied spectrophotometrically. The kinetic parameters and the rate constant values show the following acceptor tendency trend for the diorganotin(IV)dichlorides: Ph2SnCl2> Me2SnCl2> Bu2SnCl2. Adducts have been separately synthesized and fully characterized by 119SnNMR, IR, UV–vis spectra, and elemental microanalysis (C,H,N) methods. The trend of the rate constants for the adduct formation of the cobalt complexes with a given tin acceptor decreases as follow: Co(amaen) > Co(ampen) > Co(campen). The linear plots of kobs vs. the molar concentration of the diorganotin(IV)dichlorides, the high span of the second‐order rate constant k2 values, and the large negative values of AS≠ suggest an associative (A) mechanism for the acceptor–donor adduct formation. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 499–507, 2010 相似文献
2.
Donor property of cobalt(II) Schiff base complexes toward triphenyltin(IV)‐chloride: A kinetic study
In this study, some cobalt(II)tetraaza Schiff base complexes were used as donors in coordinating to triphenyltin(IV)chloride as acceptors; the kinetics and mechanism of the adduct formation were studied spectrophotometrically. Co(II)tetraaza Schiff base complexes used were [Co(amaen)][N,N′‐ethylene‐bis‐(o‐amino‐α‐methylbenzylideneiminato)cobalt(II)] ( 1 ), [Co(appn)] [N,N′‐1,2‐propylene‐bis‐(o‐amino‐α‐phenylbenzylideneiminato)cobalt(II)] ( 2 ), [Co(ampen)] [N,N′‐ethylene‐bis‐(o‐amino‐α‐phenylbenzylideneiminato)cobalt‐(II)] ( 3 ), [Co(cappn)][N,N′‐1,2‐proylene‐bis‐(5‐chloro‐o‐amino‐α‐phenylbenzylideneiminato)cobalt(II)] ( 4 ), and [Co(campen)] [N,N′‐ethylene‐bis‐(5‐chloro‐o‐amino‐α‐phenylbenzylid‐eneiminato)cobalt(II)] ( 5 ). The reactivity trend of the complexes in interaction with triphenyltin(IV)chloride was Co(amaen) > Co(appn) > Co(ampen) > Co(cappn) > Co(campen). The linear plots of kobs versus the molar concentration of the triphenyltin(IV)chloride, a high span of the second‐order rate constant k2 values, and large negative values of ΔS≠ and low ΔH≠ values suggest an associative (A) mechanism for the acceptor–donor adduct formation. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 635–640, 2012 相似文献
3.
Natthaya Meundaeng Timothy John Prior Apinpus Rujiwatra 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(9):1319-1326
The crystal structures of five new transition‐metal complexes synthesized using thiazole‐2‐carboxylic acid (2‐Htza), imidazole‐2‐carboxylic acid (2‐H2ima) or 1,3‐oxazole‐4‐carboxylic acid (4‐Hoxa), namely diaquabis(thiazole‐2‐carboxylato‐κ2N,O)cobalt(II), [Co(C4H2NO2S)2(H2O)2], 1 , diaquabis(thiazole‐2‐carboxylato‐κ2N,O)nickel(II), [Ni(C4H2NO2S)2(H2O)2], 2 , diaquabis(thiazole‐2‐carboxylato‐κ2N,O)cadmium(II), [Cd(C4H2NO2S)2(H2O)2], 3 , diaquabis(1H‐imidazole‐2‐carboxylato‐κ2N3,O)cobalt(II), [Co(C4H2N2O2)2(H2O)2], 4 , and diaquabis(1,3‐oxazole‐4‐carboxylato‐κ2N,O4)cobalt(II), [Co(C4H2NO3)2(H2O)2], 5 , are reported. The influence of the nature of the heteroatom and the position of the carboxyl group in relation to the heteroatom on the self‐assembly process are discussed based upon Hirshfeld surface analysis and used to explain the observed differences in the single‐crystal structures and the supramolecular frameworks and topologies of complexes 1 – 5 . 相似文献
4.
Shao‐Ming Ying Xiao‐Hui Huang Wu‐Kui Luo Yan‐Chun Xiao 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(4):375-378
Two homochiral coordination polymers based on a chiral reduced Schiff base ligand, namely poly[(μ5‐4‐{[(NR,1S)‐(1‐carboxylato‐2‐phenylethyl)amino]methyl}benzoato)zinc(II)], [Zn(C17H15NO4)]n, (1), and poly[(μ5‐4‐{[(NR,1S)‐(1‐carboxylato‐2‐phenylethyl)amino]methyl}benzoato)cobalt(II)], [Co(C17H15NO4)]n, (2), have been obtained by hydrothermal methods and studied by single‐crystal X‐ray diffraction, elemental analyses, powder X‐ray diffraction, thermogravimetric analysis, IR spectroscopy and fluorescence spectroscopy. Compounds (1) and (2) are isostructural and crystallize in the P212121 space group. Both display a three‐dimensional network structure with a one‐dimensional channel, with the benzyl group of the ligand directed towards the channel. An investigation of photoluminescence properties shows that compound (1) displays a strong emission in the purple region. 相似文献
5.
Hong‐Tao Zhang Xiao‐Zeng You 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(8):m313-m314
The asymmetric unit of the title one‐dimensional coordination polymer, catena‐poly[[μ‐pyridine‐2,3‐dicarboxylato‐1κO:2κ2N,O′‐bis[diaquacobalt(II)]]‐μ‐pyridine‐2,3‐dicarboxylato‐1κ2N,O:2κO′:1′κO′], [Co(C7H3NO4)(H2O)2]n, is composed of a cobalt(II) ion, a pyridine‐2,3‐dicarboxylate dianion and two water molecules. The polymer has a zigzag structure consisting of a chain of edge‐fused rings, and the polymer chains are linked by O—H⃛O hydrogen bonds into a three‐dimensional framework. 相似文献
6.
Dmytro S. Nesterov Volodymyr N. Kokozay Brian W. Skelton 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(6):m246-m248
The crystal structure of the title compound, triacetato‐1κO;3κ4O,O′‐(2,2′‐iminodiethanol)‐1κ3O,N,O′‐bis(μ‐2,2′‐iminodiethanolato)‐1κ2O:2κ6O,N,O′:3κ2O′‐cobalt(III)copper(II)zinc(II), [CoCuZn(C4H9NO2)2(C2H3O2)3(C4H11NO2)], shows a molecule with a triangular three‐metal core. The metal sites were refined with full occupancies, but the possibility that the Zn and Cu positions are actually mixed Cu/Zn sites cannot be excluded. The intermetallic Cu⋯Co and Co⋯Zn distances are 2.924 (3) and 2.906 (3) Å, respectively. The neutral molecules are held together by N—H⋯O hydrogen bonds involving amine groups from the 2,2′‐iminodiethanol ligands and acetate groups to build two‐dimensional layers. 相似文献
7.
Agnieszka Czapik Maria Gdaniec 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(9):m257-m262
The reaction of cobalt(II) nitrate hexahydrate with dimethylglyoxime (DMGH2) and 1,10‐phenanthroline (phen) in a 1:1:2 molar ratio results in two CoIII mono‐dimethylglyoximates having two chelating phen ligands in cis positions and the CoIII atom coordinated by six N atoms in a distorted octahedral coordination geometry. The isolated products differ in the deprotonation state of the DMGH2 ligand. In [μ‐hydrogen bis(N,N′‐dioxidobutane‐2,3‐diimine)]tetrakis(1,10‐phenanthroline)cobalt(III) trinitrate ethanol disolvate 1.87‐hydrate, [Co2(C4H6N2O2)(C4H7N2O2)(C12H8N2)4](NO3)3·2C2H6O·1.87H2O, (I), the C2‐symmetric cation is formed with the coordination [Co(DMG)(phen)2]+ cations aggregating via a very strong O−...H+...O− hydrogen bond with an O...O distance of 2.409 (4) Å. Crystals of (I) exhibit extensive disorder of the solvent molecules, the nitrate anions and one of the phen ligands. Compound (I) is a kinetic product, not isolated previously from similar systems, that transforms slowly into (N‐hydroxy‐N′‐oxidobutane‐2,3‐diimine)bis(1,10‐phenanthroline)cobalt(III) dinitrate ethanol monosolvate 0.4‐hydrate, [Co(C4H7N2O2)(C12H8N2)2](NO3)2·C2H6O·0.40H2O, (II), with the DMGH− ligand hydrogen bonded to one of the nitrate anions. In (II), the solvent molecules and one of the nitrate anions are disordered. 相似文献
8.
Masood Parvez Kristin Braitenbach 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(8):919-920
The structure of dichloro[1‐(p‐chlorobenzyl)‐2‐(1‐pyrrolidinylmethyl‐N)‐1,3‐benzimidazole‐N3]cobalt(II), [CoCl2(C19H20ClN3)], contains a molecule of clemizole bound in a bidentate manner to cobalt through its imidazole and pyrrolidinyl N atoms, with significantly different Co—N distances of 1.976 (5) and 2.126 (5) Å, respectively. The geometry around cobalt is distorted tetrahedral, with significantly different Co—Cl distances of 2.217 (2) and 2.233 (2) Å, and the pyrrolidinyl ring is disordered. 相似文献
9.
Yanfeng Cui Yameng Xu Xin Liu Yahong Li Bao‐Lin Wang Yaping Dong Wu Li Shiming Lei 《化学:亚洲杂志》2019,14(15):2620-2628
The employment of a new rigid N‐tridentate ligand, bis(1‐chloroimidazo[1,5‐a]pyridin‐3‐yl)pyridine (bcpp), in the construction of cobalt(II) single‐ion magnets is reported. Two cobalt(II) complexes, [Co(bcpp)Cl2] ( 1 ) and [Co(bcpp)Br2] ( 2 ), have been prepared and characterized. Single‐crystal XRD analyses reveal that complexes 1 and 2 are isostructural. They are pentacoordinated mononuclear cobalt(II) compounds with expected trigonal bipyramidal geometry. Both analysis of the magnetic data and ab initio calculations reveal easy‐plane magnetic anisotropy (D>0) for 1 and 2 . Detailed alternating current magnetic susceptibility measurements reveal the occurrence of slow magnetic relaxation behavior for the cobalt(II) centers of 1 and 2 ; thus indicating that both complexes are field‐induced single‐ion magnets. 相似文献
10.
Jian‐Fang Ma Jin Yang Jing‐Fu Liu 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(8):m304-m306
The self‐assembly of three crystallographically distinct fumarate ions, two unique cobalt(II) ions and two unique o‐phen;anthroline molecules results in a two‐dimensional polymeric structure with the formula [Co2(C4H2O4)2(C12H8N2)2]n, namely di‐μ‐fumatato‐bis(o‐phenanthroline)dicobalt(II). The Co atoms are at the nodes of a two‐dimensional array linked by coordinated fumarate ligands. Each Co atom is coordinated in a distorted octahedral manner to four fumarate O atoms and two N atoms from the chelating phenanthroline ligands. 相似文献
11.
Guo‐Hua Wei Jin Yang Jian‐Fang Ma Ying‐Ying Liu Shun‐Li Li 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(7):m267-m270
In the cobalt(II) coordination polymer poly[[(μ2‐benzene‐1,3‐dicarboxylato){μ2‐1,1′‐[2,2′‐oxybis(ethane‐2,1‐diyl)]di‐1H‐imidazole}cobalt(II)] monohydrate], {[Co(C10H14N4O)(C8H4O4)]·H2O}n, two crystallographically distinct CoII cations are four‐coordinated by N2O2 donor sets in distorted tetrahedral geometries. The CoII centers are connected by benzene‐1,3‐dicarboxylate (m‐BDC) anions, giving two types of linear chains, which are further joined via meso‐helical 1,1′‐[2,2′‐oxybis(ethane‐2,1‐diyl)]di‐1H‐imidazole ligands to yield a thick two‐dimensional slab. The compound displays a two‐dimensional four‐connected 42.63.8 topology, which is unprecedented in coordination polymers. 相似文献
12.
《Journal of Coordination Chemistry》2012,65(4):433-444
Abstract Spectroscopic changes observed on addition of nitrite to solutions of cobalt(II) tetra-sulfophthalocyanine ([Co(II)TSPc]4-) in the presence of N? 3 or ClO? 4 are reported. There is spectroscopic evidence for the oxidation of [Co(II)TSPc]4- to a [Co(III)TSPc]3- species in the presence of nitrite ions. Equilibrium and kinetic studies for the interaction between [Co(II)TSPc]4- and NO? 2 are reported. The rate was found to be first order in both [Co(II)TSPc]4- and NO? 2. The rate constant for the forward reaction, k f=1.6 × 10?4 dm3mol?1s?1 was determined at 20°C for the interaction between nitrite ions and [Co(II)TSPc]4- in the presence of NO3 ? or ClO4 ? ions. 相似文献
13.
Zhong‐Lu You 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(6):m295-m297
The two title complexes, catena‐poly[[{2,2′‐[1,3‐propanediylbis(nitrilomethylidyne)]diphenolato}cobalt(III)]‐μ‐azido], [Co(C17H16N2O2)(N3)]n, (I), and catena‐poly[[{2,2′‐[1,3‐propanediylbis(nitrilomethylidyne)]diphenolato}cobalt(III)]‐μ‐thiocyanato], [Co(C17H16N2O2)(NCS)]n, (II), are isomorphous polynuclear cobalt(III) compounds. In both structures, the CoIII atom is six‐coordinated in an octahedral configuration by two N atoms and two O atoms of one Schiff base, and two terminal N or S atoms from two bridging ligands. The [N,N′‐bis(salicylidene)propane‐1,3‐diaminato]cobalt(III) moieties are linked by the bridging ligands, viz. azide in (I) and thiocyanate in (II), giving zigzag polymeric chains with backbones of the type [–Co—N—N—N—Co]n in (I) or [–Co—N—C—S—Co]n in (II) running along the c axis. 相似文献
14.
A Two‐Coordinate Cobalt(II) Imido Complex with NHC Ligation: Synthesis,Structure, and Reactivity 下载免费PDF全文
Jingzhen Du Linbo Wang Prof. Dr. Meihua Xie Prof. Dr. Liang Deng 《Angewandte Chemie (International ed. in English)》2015,54(43):12640-12644
The synthesis, structural characterization, and reactivity of the first two‐coordinate cobalt complex featuring a metal–element multiple bond [(IPr)Co(NDmp)] ( 4 ; IPr=1,3‐bis(2′,6′‐diisopropylphenyl)imidazole‐2‐ylidene; Dmp=2,6‐dimesitylphenyl) is reported. Complex 4 was prepared from the reaction of [(IPr)Co(η2‐vtms)2] (vtms=vinyltrimethylsilane) with DmpN3. An X‐ray diffraction study revealed its linear C? Co? N core and a short Co? N distance (1.691(6) Å). Spectroscopic characterization and calculation studies indicated the high‐spin nature of 4 and the multiple‐bond character of the Co? N bond. Complex 4 effected group‐transfer reactions to CO and ethylene to form isocyanide and imine, respectively. It also facilitated E? H (E=C, Si) σ‐bond activation of terminal alkyne and hydrosilanes to produce the corresponding cobalt(II) alkynyl and cobalt(II) hydride complexes as 1,2‐addition products. 相似文献
15.
Jingzhen Du Linbo Wang Meihua Xie Liang Deng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(43):12831-12835
The synthesis, structural characterization, and reactivity of the first two‐coordinate cobalt complex featuring a metal–element multiple bond [(IPr)Co(NDmp)] ( 4 ; IPr=1,3‐bis(2′,6′‐diisopropylphenyl)imidazole‐2‐ylidene; Dmp=2,6‐dimesitylphenyl) is reported. Complex 4 was prepared from the reaction of [(IPr)Co(η2‐vtms)2] (vtms=vinyltrimethylsilane) with DmpN3. An X‐ray diffraction study revealed its linear C Co N core and a short Co N distance (1.691(6) Å). Spectroscopic characterization and calculation studies indicated the high‐spin nature of 4 and the multiple‐bond character of the Co N bond. Complex 4 effected group‐transfer reactions to CO and ethylene to form isocyanide and imine, respectively. It also facilitated E H (E=C, Si) σ‐bond activation of terminal alkyne and hydrosilanes to produce the corresponding cobalt(II) alkynyl and cobalt(II) hydride complexes as 1,2‐addition products. 相似文献
16.
《Journal of Coordination Chemistry》2012,65(8):1426-1435
A new water-soluble Co(II) Schiff-base complex, sodium[{N,N′-bis(5-sulfosalicylidene)-1,8-diamino-3,6-dioxaoctan}cobalt] dihydrate, abbreviated as Na2[Co(II)L], was synthesized and characterized. The formation constants and thermodynamic parameters for the interaction of this complex with imidazole (Im) and 1-methylimidazole (MeIm) were determined spectroscopically in aqueous solution, ethanol/water (10/90), and methanol/water (10/90) under physiological conditions (pH?=?7), constant ionic strength (I?=?0.1?mol?dm?3 KNO3), and various temperatures ranging from 294 to 310?K. Our spectroscopic and thermodynamic results show that this adduct formation is endothermic and the positive values of ΔS f° make ΔG f° negative. The trend in variation of ΔH f° and ΔS f° for Im is in the order water?>?methanol?>?ethanol, but for MeIm it is in the opposite order which is related to the hydrogen bonding between solvents and these donors. Formation constants between MeIm and Na2[Co(II)L] in these three solvents are larger than for Im which depends on the electron donation of methyl on MeIm. 相似文献
17.
Alex S. Ionkin William J. Marshall Douglas J. Adelman Aaron L. Shoe Rupert E. Spence Tuyu Xie 《Journal of polymer science. Part A, Polymer chemistry》2006,44(8):2615-2635
A new series of nitro‐substituted bis(imino)pyridine ligands {2,6‐bis[1‐(2‐methyl‐4‐nitrophenylimino)ethyl]pyridine, 2,6‐bis[1‐(4‐nitrophenylimino)ethyl]pyridine, (1‐{6‐[1‐(4‐nitro‐phenylimino)‐ethyl]‐pyridin‐2‐yl}‐ethylidene)‐(2,4,6‐trimethyl‐phenyl)‐amine, and 2,6‐bis[1‐(2‐methyl‐3‐nitrophenylimino)ethyl]pyridine} and their corresponding Fe(II) complexes [{p‐NO2? o‐Me? Ph? N?C(Me)? Py? C(Me)?N? Ph? o‐ Me? p‐NO2}FeCl2 ( 10 ), L2FeCl2 ( 11 ), {m‐NO2? o‐Me? Ph? N?C(Me)? Py? C(Me)?N? Ph? o‐Me? m‐NO2}FeCl2 ( 12 ), and {p‐NO2? Ph? N?C(Me)? Py? C(Me)?N? Mes}FeCl2 ( 14 )] were synthesized. According to X‐ray analysis, there were shortenings of the axial Fe? N bond lengths (up to 0.014 Å) in para‐nitro‐substituted complex 10 and (up to 0.015 Å) in meta‐nitro‐substituted complex 12 versus the Fe(II) complex without nitro groups [{o‐Me? Ph? N?C(Me)? Py? C(Me)?N? Ph? o‐Me}FeCl2 ( 1 )]. Complexes 10 , 12 , and 14 afforded very active catalysts for the production of α‐olefins and were more temperature‐stable and had longer lifetimes than parent non‐nitro‐substituted Fe(II) complex 1 . The reaction between FeCl2 and a sterically less hindered ligand [p‐NO2? Ph? N?C(Me)? Py? C(Me)?N? Ph? p‐NO2] resulted in the formation of octahedral complex 11 . A para‐dialkylamino‐substituted bis(imino)pyridine ligand [p‐NEt2? o‐Me? Ph? N?C(Me)? Py? C(Me)?N? Ph? o‐Me? p‐NEt2] and the corresponding Fe(II) complex [{p‐NEt2? o‐Me? Ph? N?C(Me)? Py? C(Me)?N? Ph? o‐Me? p‐NEt2}FeCl2 ( 16 )] were synthesized to evaluate the effect of enhanced electron donation of the ligand on the catalytic performance. According to X‐ray analysis, there was a shortening (up to 0.043 Å) of the axial Fe? N bond lengths in para‐diethylamino‐substituted complex 16 in comparison with parent Fe(II) complex 1 . © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2615–2635, 2006 相似文献
18.
Doyle Britton 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(1):o14-o16
The structures of o‐chlorobenzonitrile, C7H4ClN, (I), and o‐bromobenzonitrile, C7H4BrN, (II), have similar packing arrangements, even though Z′ = 4 in (I) and Z′ = 1 in (II). Both structures involve X⋯N interactions, as well as weak C—H⋯X and C—H⋯N hydrogen bonds. The four crystallographically independent molecules in (I) are related by pseudosymmetry. 相似文献
19.
Ladislav Bohatý Michel Fleck 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(1):m22-m26
In the crystal structures of the title compounds, hexaaquacobalt(II) tetraaquadiglycinatocobalt(II) bis(sulfate), [Co(H2O)6][Co(C2H5NO2)2(H2O)4](SO4)2, (I), poly[diaqua‐μ3‐glycinato‐di‐μ4‐thiosulfato‐tetrasodium(I)], [Na4(C2H5NO2)(S2O3)2(H2O)2]n, (II), and poly[μ2‐glycinato‐μ4‐thiosulfato‐dipotassium(I)], [K2(C2H5NO2)(S2O3)]n, (III), all atoms are located on general positions, except the Co atoms in (I), which are located on inversion centres. In (I), hydrogen bonds play an important role, while the alkali thiosulfate compounds are characterized by three‐dimensional frameworks of polyhedra. Relations to other compounds of glycine and metal sulfates are commented on. 相似文献
20.
For a long time, the cobalt(II) complex ([Co(napy)4](ClO4)2) (napy=1, 8‐naphthyridine) has been considered as an eight‐coordinate complex without any structural proof. After careful considerations, two complexes [Co(napy)2Cl2] ( 1 ) and [Co(napy)4](ClO4)2 ( 2 ) based on the bidentate ligand napy were synthesized and structurally characterized. X‐ray single‐crystal structural determination showed that the cobalt(II) center in [Co(napy)2Cl2] ( 1 ) is four‐coordinate with a tetrahedral geometry (Td), while [Co(napy)4](ClO4)2 ( 2 ) is seven‐coordinate rather than eight‐coordinate with a capped trigonal prism geometry (C2v). Direct‐current (dc) magnetic data revealed that complexes 1 and 2 possess positive zero‐field splitting (ZFS) parameters of 11.08 and 25.30 cm?1, respectively, with easy‐plane magnetic anisotropy. Alternating current(ac) susceptibility measurements revealed that both complexes showed slow magnetic relaxation behaviour. Theoretical calculations demonstrated that the presence of easy‐plane magnetic anisotropy (D>0) for complexes 1 and 2 is in agreement with the experimental data. Furthermore, these results pave the way to obtain four‐coordinate and seven‐coordinate cobalt(II) single‐ion magnets (SIMs) by using a bidentate ligand. 相似文献