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1.
Cu4P4X4Fe2 (X = Cl, Br) cages are formed upon reactions of octaethyl‐1,1′‐diphosphaferrocene (odpf) with the respective CuI halide in CH2Cl2/CH3CN solvent mixtures. These cages have adamantoid Cu4X4P2 cores with two planar anelated CuP2Fe rings as the flaps. Both complexes 1 and 2 feature tri‐ and tetracoordinate CuI ions and an additional acetonitrile solvent molecule in the crystal. In 1 , the solvent molecule is coordinated to one copper ion whereas it remains uncoordinated in 2 . The tricoordinate CuI ions show a slight pyramidalization at the metal atom and somewhat short contacts to the other tricoordinate CuI ion in 2 or the Cu3‐triangle in 1 . NMR spectroscopy revealed easy decoordination of the acetonitrile ligand from 1 and a dynamic “windshield‐wiper”‐type process that interconverts the differently coordinated phospholide rings of each odpf ligand and the tri‐ and tetracoordinate CuI ions. 相似文献
2.
Xiaoming Liu Colin A. Kilner Malcolm A. Halcrow 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(3):m100-m102
The title compound, [Cu4Cl6O(C12H14N2)4], is a new example of the well known [Cu4(μ4‐O)(μ‐X)6L4] class of complex (X− is Cl−, Br− or I−, and L is a monodentate ligand). The molecule has crystallographic C2 symmetry, with two Cl− ions on each edge of a Cu4 tetrahedron. Two of these, on opposite edges of the tetrahedron, accept intramolecular hydrogen bonds from two of the pyrazole N—H donors. 相似文献
3.
Glria Esquius Josefina Pons Ramn Yez Josep Ros Xavier Solans Merc Font‐Bardia 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(2):m133-m134
In the title compound, [Rh2(C8H15N3)2(C8H12)2]Cl2·CH2Cl2·CH3OH, the dinuclear RhI complex has C2 symmetry and the two pyrazolato ligands act as μ‐bridges. The coordination of each RhI cation is completed by one cyclooctadiene (COD) ligand. It is shown that the average Rh—C(COD) distance is linearly dependent on the Rh—N(pyrazole) distance in this type of compound, and this is ascribed to the steric hindrance produced by the packing. 相似文献
4.
Visible‐Light‐Accelerated Copper(II)‐Catalyzed Regio‐ and Chemoselective Oxo‐Azidation of Vinyl Arenes 下载免费PDF全文
M. Sc. Asik Hossain Dr. Adiyala Vidyasagar M. Sc. Christian Eichinger Dr. Christian Lankes M. Sc. Jenny Phan Prof. Dr. Julia Rehbein Prof. Dr. Oliver Reiser 《Angewandte Chemie (International ed. in English)》2018,57(27):8288-8292
The visible‐light‐accelerated oxo‐azidation of vinyl arenes with trimethylsilylazide and molecular oxygen as stoichiometric oxidant was achieved. In contrast to photocatalysts based on iridium, ruthenium, or organic dyes, [Cu(dap)2]Cl or [Cu(dap)Cl2] were found to be unique for this transformation, which is attributed to their ability to interact with the substrates through ligand exchange and rebound mechanisms. CuII is proposed as the catalytically active species, which upon coordinating azide will undergo light‐accelerated homolysis to form CuI and azide radicals. This activation principle (CuII‐X→CuI+X.) opens up new avenues for copper‐based photocatalysis. 相似文献
5.
Mohammad Hossein Habibi Morteza Montazerozohori Kazem Barati Ross W. Harrington William Clegg 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(12):m592-m594
The 1:1 adduct of N,N′‐bis(2‐chlorobenzylidene)ethylenediamine (cb2en) with copper(I) chloride proves to be an ionic compound with CuI‐centred cations and anions, [Cu(C16H14Cl2N2)2][CuCl2]·CH3CN. In the cation, the CuI atom has a flattened tetrahedral coordination geometry, with a small bite angle for the chelating ligands, which form a double‐helical arrangement around the metal centre. The anion is almost linear, as expected. The packing of the cations involves intermolecular π–π interactions, which lead to columns of translationally related cations along the shortest unit‐cell axis, with anions and solvent molecules in channels between them. 相似文献
6.
Tünde Tunyogi Andrea Dek 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(5):m133-m136
The dinuclear AuI complex containing the 4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene (xantphos) ligand and trifluoroacetate anions exists in a solvent‐free form, [μ‐4,5‐bis(diphenylphosphino)‐9,9‐dimethylxanthene]bis[(trifluoroacetato)gold(I)], [Au2(C2F3O2)2(C39H32OP2)], (I), and as a dichloromethane solvate, [Au2(C2F3O2)2(C39H32OP2)]·0.58CH2Cl2, (II). The trifluoroacetate anions are coordinated to the AuI centres bridged by the xantphos ligand in both compounds. The AuI atoms are in distorted linear coordination environments in both compounds. The phosphine substituents are in a syn arrangement in the xantphos ligand, which facilitates the formation of short aurophilic Au...Au interactions of 2.8966 (8) Å in (I) and 2.9439 (6) Å in (II). 相似文献
7.
Mwaffak Rukiah Mahmoud Al‐Ktaifani 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(3):m135-m138
In order to explore the chemistry of the bidentate ligand 2,2‐dimethylpropane‐1,3‐diyl diisocyanide and to investigate the effect of counter‐ions on the polymeric structure of (2,2‐dimethylpropane‐1,3‐diyl diisocyanide)silver(I) complexes, the title polymeric compound, [AgI(C7H10N2)]n, was synthesized by treatment of 2,2‐dimethylpropane‐1,3‐diyl diisocyanide with AgI. X‐ray powder diffraction studies show, as expected, a polymeric structure, similar to the very recently reported Cl− and NO3− analogues [AgX(C7H10N2)]n (X = Cl− or NO3−). In the title structure, the AgI centre is bridged to two adjacent AgI neighbours by bidentate 2,2‐dimethylpropane‐1,3‐diyl diisocyanide ligands via the NC groups to form [Ag{CNCH2C(CH3)2CH2NC}]n chains. The iodide counter‐ions crosslink the AgI centres of the chains to form a two‐dimensional polymeric {[Ag{CNCH2C(CH3)2CH2NC}]I}n network. This study also shows that this bidentate ligand forms similar polymeric structures on treatment with AgX, regardless of the nature of the counter‐ion X−, and also has a strong tendency to form polymeric complexes rather than dimeric or trimeric ones. 相似文献
8.
Zhiyong Wu Duanjun Xu Jingyun Wu Michael Y. Chiang 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):m374-m376
The title compound, [CuCl(CH4N2S)2]·2C11H6N2O·H2O, consists of molecules of a CuI–thiourea complex, free 4,5‐diazafluoren‐9‐one (dafone) and crystalline water. The planar complex molecule has trigonal coordination geometry around the CuI atom. The dafone and water molecules, which are hydrogen bonded to the CuI complex, are approximately coplanar with this complex. The crystal displays a sheet structure and π–π stacking is observed between neighbouring sheets. 相似文献
9.
Almudena Amoedo‐Portela Rosa Carballo Jos S. Casas Emilia García‐Martínez Concepcin Gmez‐Alonso Angeles Snchez‐Gonzlez Jos Sordo Ezequiel M. Vzquez‐Lpez 《无机化学与普通化学杂志》2002,628(5):939-950
Bis(2‐pyridylthio)methane [bpytm, (pyS)2CH2] and complexes of this ligand with ZnII, HgII, CuI, and AgI have been prepared and characterised by elemental analysis, by IR, Raman and 1H and 13C NMR spectroscopy, and by X‐ray diffractometry. The ligand is N, N′‐didentate in the ZnII complexes; N‐monodentate in one HgII complex and N, N′‐bis(monodentate) in the other; N‐mono‐N′, S‐didentate in the CuI complex; and N, S′‐bis(mono)‐N′, S‐didentate in the AgI complex. The structural parameters of the ligand in each coordination mode are compared with those of the free ligand and those of the triiodide salt of the protonated ligand. 相似文献
10.
Malcolm A. Halcrow Colin A. Kilner Mark Thornton‐Pett 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(6):711-713
The title compound, [Cu(C27H40BN6)2]·2CH2Cl2, contains a four‐coordinate CuII ion lying on a crystallographic inversion centre, giving rise to a near‐regular square‐planar stereochemistry. There is an axial contact of 2.71 Å between the Cu ion and ligand B—H group, although this is unlikely to correspond to a significant `agostic' interaction. 相似文献
11.
Xiao‐Li Gao Yi‐Bin Wei Yan‐Ping Li Pin Yang 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(1):m10-m12
In the title compound, [CuCl(C6H6N4)(H2O)][Cu(C4H5NO4)Cl]·H2O, the CuII atom in the cation is coordinated by one Cl− ion, two N atoms of the 2,2′‐biimidazole ligand and one aqua ligand. Within the anion, the CuII atom is bonded to one Cl− ion, and one N and two O atoms of the iminodiacetate ligand. Neighbouring cations and anions are connected to each other by Cu·Cl semi‐coordination bonds of 2.830 (12) and 3.071 (12) Å, forming a Cu2Cl2 rectangular unit. The dinuclear units further link into a polymeric chain along the a axis through Cu·Oaqua interactions of 2.725 (3) Å. Including the long coordination bonds, the geometries around the Cu atoms in the cation and anion are square‐pyramidal and distorted octahedral, respectively. 相似文献
12.
Sonja Herres‐Pawlis Dr. Tarimala Seshadri Ulrich Flörke Gerald Henkel Prof. Dr. 《无机化学与普通化学杂志》2009,635(8):1209-1214
The reaction of 2,2′‐Bis(2N‐(1,1′,3,3′‐tetramethyl‐guanidino))diphenylene‐amine (TMG2PA) ( 1 ) with CuI in MeCN results in the formation of [CuII(TMG2PAamid)I] ( 2 ) indicatingthat CuI is the target of an oxidative attack of the N‐H proton of the ligand which itself is converted to molecular hydrogen. In contrast, if [Cu(MeCN)4][PF6] is used as the CuI source, [CuI2(TMGbenz)2][PF6]2 ( 3 ) is obtained instead. The use of the non‐coordinating counterion [PF6]– apparently prevents CuI from oxidation but induces itself a cyclisation reaction within the ligand which results in the formation of a benzimidazole‐guanidine ligand. 相似文献
13.
Graham A. Bowmaker Prof. Dr. Michael I. Bruce Brian W. Skelton Neil Somers Allan H. White 《无机化学与普通化学杂志》2007,633(7):1024-1030
The complexes [Cu2Br4]2?, [Cu2I4]2?, [Cu2I2Br2]2?, [Cu2I3Cl]2?, [Ag2Cl4]2? have been characterized as their isomorphous bis(triphenylphosphoranylidene)ammonium ([Ph3PNPPh3]+ = PNP+) salts by single crystal structural determinations. All anions show the centrosymmetric doubly halogen‐bridged forms [XM(μ‐X)2MX]2? with three‐coordinate metal atoms that have been observed in [M2X4]2? complexes with other large organic cations. In [Cu2I2Br2]2? the iodide ligands occupy the bridging positions and the bromide the terminal positions, while in [Cu2I3Cl]2?, obtained in an attempt to prepare [Cu2I2Cl2]2?, two of the iodide ligands occupy the bridging positions with the third iodide and the chloride ligand occupying two statistically disordered terminal positions. In [Ag2Cl4]2? the distortion from ideal trigonal coordination of the metal atom is greater than in the copper complexes, but less than in other previously reported [Ag2Cl4]2? complexes with organic cations. The ν(MX) bands have been assigned in the far‐IR spectra, and confirm previous observations regarding the unexpectedly simple IR spectra of [Cu2X4]2? complexes. 相似文献
14.
Copper(II) and Sodium(I) Complexes based on 3,7‐Diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane‐5‐oxide: Synthesis,Characterization, and Catalytic Activity 下载免费PDF全文
《化学:亚洲杂志》2018,13(19):2868-2880
The reaction of 3,7‐diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane (DAPTA) with metal salts of CuII or NaI/NiII under mild conditions led to the oxidized phosphane derivative 3,7‐diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane‐5‐oxide (DAPTA=O) and to the first examples of metal complexes based on the DAPTA=O ligand, that is, [CuII(μ‐CH3COO)2(κO‐DAPTA=O)]2 ( 1 ) and [Na(1κOO′;2κO‐DAPTA=O)(MeOH)]2(BPh4)2 ( 2 ). The catalytic activity of 1 was tested in the Henry reaction and for the aerobic 2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPO)‐mediated oxidation of benzyl alcohol. Compound 1 was also evaluated as a model system for the catechol oxidase enzyme by using 3,5‐di‐tert‐butylcatechol as the substrate. The kinetic data fitted the Michaelis–Menten equation and enabled the obtainment of a rate constant for the catalytic reaction; this rate constant is among the highest obtained for this substrate with the use of dinuclear CuII complexes. DFT calculations discarded a bridging mode binding type of the substrate and suggested a mixed‐valence CuII/CuI complex intermediate, in which the spin electron density is mostly concentrated at one of the Cu atoms and at the organic ligand. 相似文献
15.
Katherine A. Bussey Annie R. Cavalier Jennifer R. Connell Margaret E. Mraz Kayode D. Oshin Tomislav Pintauer Allen G. Oliver 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(7):526-533
The structures of five compounds consisting of (prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine complexed with copper in both the CuI and CuII oxidation states are presented, namely chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(I) 0.18‐hydrate, [CuCl(C15H17N3)]·0.18H2O, (1), catena‐poly[[copper(I)‐μ2‐(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ5N,N′,N′′:C2,C3] perchlorate acetonitrile monosolvate], {[Cu(C15H17N3)]ClO4·CH3CN}n, (2), dichlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II) dichloromethane monosolvate, [CuCl2(C15H17N3)]·CH2Cl2, (3), chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II) perchlorate, [CuCl(C15H17N3)]ClO4, (4), and di‐μ‐chlorido‐bis({(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II)) bis(tetraphenylborate), [Cu2Cl2(C15H17N3)2][(C6H5)4B]2, (5). Systematic variation of the anion from a coordinating chloride to a noncoordinating perchlorate for two CuI complexes results in either a discrete molecular species, as in (1), or a one‐dimensional chain structure, as in (2). In complex (1), there are two crystallographically independent molecules in the asymmetric unit. Complex (2) consists of the CuI atom coordinated by the amine and pyridyl N atoms of one ligand and by the vinyl moiety of another unit related by the crystallographic screw axis, yielding a one‐dimensional chain parallel to the crystallographic b axis. Three complexes with CuII show that varying the anion composition from two chlorides, to a chloride and a perchlorate to a chloride and a tetraphenylborate results in discrete molecular species, as in (3) and (4), or a bridged bis‐μ‐chlorido complex, as in (5). Complex (3) shows two strongly bound Cl atoms, while complex (4) has one strongly bound Cl atom and a weaker coordination by one perchlorate O atom. The large noncoordinating tetraphenylborate anion in complex (5) results in the core‐bridged Cu2Cl2 moiety. 相似文献
16.
Rongqing Li Pusu Zhao Guodong Tang Xiaoling Tang 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(10):m339-m341
The title compound, [Cu2(C13H14N3)2Cl2], is a neutral dimeric copper(II) complex. The two CuII atoms are asymmetrically bridged by two chloride ions. Each CuII atom is also bound to the three N atoms of a deprotonated tridentate Schiff base ligand, giving a distorted square‐pyramidal N3Cl2 coordination environment overall. The dinuclear complex lies across an inversion centre in the space group P. This work demonstrates the effect of ligand flexibility and steric constraints on the structures of copper(II) complexes. 相似文献
17.
Jun‐Feng Zhang Xin Gan Quan‐Qing Xu Jian‐Hua Chen Mei Yuan Wen‐Fu Fu Prof. Dr. 《无机化学与普通化学杂志》2007,633(10):1718-1722
The reactions of pyrimidine‐phosphine ligand N‐[(diphenylphosphino)methyl]‐2‐pyrimidinamine ( L ) with various metal salts of PtII, PdII and CuI provide three new halide metal complexes, Pt2Cl4(μ‐L)2·2CH2Cl2 ( 1 ), Pd2Cl4(μ‐L)2 ( 2 ), and [Cu2(μ‐I)2L2]n ( 3 ). Single crystal X‐ray diffraction studies show that complexes 1 and 2 display a similar bimetallic twelve‐membered ring structure, while complex 3 consists of one‐dimensional polymeric chains, which are further connected into a 2‐D supramolecular framework through hydrogen bonds. In the binuclear complexes 1 and 2 , the ligand L serves as a bridge with the N and P as coordination atoms, but in the polymeric complex 3 , both bridging and chelating modes are adopted by the ligand. The spectroscopic properties of complexes 1 ‐ 3 as well as L have been investigated, in which complex 3 exhibits intense photoluminescence originating from intraligand charge transfer (ILCT) π→π* and metal‐to‐ligand charge‐transfer (MLCT) excited states both in acetonitrile solution and solid state, respectively. 相似文献
18.
Christian Nther Inke Jeß 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(3):m190-m192
The CuI cations in the title compound, [Cu(NCS)(C6H6N2O)2]n, are coordinated by N atoms from each of two mirror‐related nicotinamide ligands, as well as by one N atom of one thiocyanate ligand and one S atom of a symmetry‐related thiocyanate ligand, within a slightly distorted tetrahedron. The CuI cations and the thiocyanate anions are located on a crystallographic mirror plane and the nicotinamide ligands occupy general positions. The CuI cations are connected by the thiocyanate anions to form chains in the direction of the crystallographic a axis. These chains are connected by hydrogen bonds between the amide H atoms and the O atoms of adjacent nicotinamide ligands, to give a three‐dimensional structure. 相似文献
19.
Cai‐Hong Chen Jiwen Cai Xiao‐Ming Chen 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(1):m59-m60
The title compound, [Cu2(C6H19N4)2Cl2](C10H6O6S2)2·5H2O, is comprised of discrete [Cu2(tren)2Cl2]2+ dimers {tren is 2‐[N,N‐bis(2‐aminoethyl)amino]ethylaminium} and naphthalene‐1,5‐disulfonate anions. Two Cl? anions bridge two CuII ions, each of which is also coordinated by two of the primary and the tertiary amino N atoms of the tren ligand, giving each metal atom a distorted square‐pyramidal coordination geometry. The cation lies about an inversion centre and the asymmetric unit also has two independent anions lying about inversion centres. 相似文献
20.
Shuhong Wu 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(6):m211-m214
In the title polymeric heterometallic compound, {[Cu3Gd(C6H4NO2)3Cl3(H2O)2]·0.5H2O}n, comprising copper(I) and gadolinium(III) cations bridged by nicotinate (nic) ligands and chloride anions, the GdIII centers display a bicapped trigonal prismatic geometry, defined by six carboxylate O atoms and two water molecules. For copper(I), one Cu center is three‐coordinated by three chloride ions and displays a trigonal–planar geometry; the other two Cu centers are four‐coordinated and display a very distorted tetrahedral geometry. The chloride anions act in μ2‐ and μ3‐bridging modes, linking the CuI ions into an infinite chain. The nic ligand exhibits a tridentate coordination mode, with the carboxylate O atoms linking to two GdIII ions and the N atom linking to one CuI ion. Thus, a novel three‐dimensional heterometallic coordination polymer is constructed from Gd–carboxylate subunits and Cu—Cl chains. In addition, intra‐ and intermolecular O—H...O and O—H...Cl hydrogen bonds are also observed within the three‐dimensional structure. Topologically, the framework represents an unusual 3,6‐connected (4.82)3(410.65) net. 相似文献