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1.
Mei Qu Fu‐Qiang Zhang Dian‐Hui Wang Huan Li Juan‐Juan Hou Xian‐Ming Zhang 《Angewandte Chemie (International ed. in English)》2020,59(16):6507-6512
The only feasible access to non‐face‐centered cubic (FCC) copper was by physical vapor deposition under high vacuum. Now, non‐FCC copper is observed in a series of alkynyl‐protected Cu53 nanoclusters (NCs) obtained from solution‐phase synthesis. Determined by single‐crystal X‐ray crystallography, the structures of Cu53(C≡CPhPh)9(dppp)6Cl3(NO3)9 and its two derivatives reveal an ABABC stacking sequence involving 41 Cu atoms. It can be regarded as a mixed FCC and HCP structure, which gives strong evidence that Cu can be arranged in non‐FCC lattice at ambient conditions when proper ligands are provided. Characterization methods including X‐ray absorption fine structure, XPS, ESI‐MS, UV/Vis, Auger spectroscopy, and DFT calculations were carried out. CuII was shown to successively coordinate with introduced ligands and changed to CuI after bonding with phosphine. The following addition of NaBH4 and the aging step further reduced it to the Cu53 NC. 相似文献
2.
Zhongfeng Li Jianbao Li Weiwei Fan Xiaonan Xue Rong Wang Yuhan Jiang Manhua Wu Qionghua Jin 《无机化学与普通化学杂志》2014,640(11):2261-2267
Six heterothiometalic clusters, namely, [WS4Cu4(dppm)4](ClO4)2 · 2DMF · MeCN ( 1 ), [MoS4Cu4(dppm)4](NO3)2 · MeCN ( 2 ) [MoS4Cu3(dppm)3](ClO4) · 4H2O ( 3 ), [WS4Cu3(dppm)3](NO3) · 4H2O ( 4 ), [WS4Cu3(dppm)3]SCN · CH2Cl2 ( 5 ), and [WS4Cu3(dppm)3]I · CH2Cl2 ( 6 ) [dppm = bis (diphenylphosphanyl)methane] were synthesized. Compounds 1 – 4 were obtained by the reactions of (NH4)2MS4 (M = Mo, W) with [Cu2(μ2‐dppm)2(MeCN)2(ClO4)2] {or [Cu(dppm)(NO3)]2} in the presence of 1,10‐phen in mixed solvent (CH3CN/CH2Cl2/DMF for 1 and 2 , CH2Cl2/CH3OH/DMF for 3 and 4 . Compounds 5 and 6 were obtained by one‐pot reactions of (NH4)2WS4 with dppm and CuSCN (or CuI) in CH2Cl2/CH3OH. These clusters were characterized by single‐crystal X‐ray diffraction as well as IR, 1H NMR, and 31P NMR spectroscopy. Structure analysis showed that compounds 1 and 2 are “saddle‐shaped” pentanuclear cationic clusters, whereas compounds 3 – 6 are “flywheel‐shaped” tetranuclear cationic clusters. In 1 and 2 , the MS42– unit (M = W, Mo) is coordinated by four copper atoms, which are further bridged by four dppm molecules. In compounds 3 – 6 , the MS42– unit is coordinated by three copper atoms and each copper atom is bridged by three dppm ligands. 相似文献
3.
Ri‐Cheng Xuan Min Xu Dong‐Ping Cheng 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(12):m587-m589
In the title compound, [CuCl2(C9H12N2O)], the CuII atom is coordinated by two Cl− anions and two N atoms of one O‐ethyl 3‐methylpyridine‐2‐carboximidic acid molecule in a slightly distorted square‐planar geometry, with Cu—N distances of 2.0483 (17) and 1.9404 (18) Å, and Cu—Cl distances of 2.2805 (10) and 2.2275 (14) Å. In addition, each CuII atom is connected by one Cl− anion and the CuII atom from a neighbouring molecule, with Cu⋯Cl and Cu⋯Cu distances of 2.9098 (13) and 3.4022 (12) Å, respectively, and, therefore, a centrosymmetric dimer is formed. Adjacent molecular dimers are connected by π–π stacking interactions between pyridine rings to form a zigzag molecular chain. The molecular chains are also enforced by N—H⋯Cl and C—H⋯Cl interactions. 相似文献
4.
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
5.
Florian Hastreiter Dr. Eugenia V. Peresypkina Dr. Alexander V. Virovets Prof. Dr. Ruth M. Gschwind Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2014,53(49):13605-13608
The reaction of [CpBnFe(η5‐P5)] ( 1 ) (CpBn=η5‐C5(CH2Ph)5) with CuI selectively yields a novel spherical supramolecule (CH2Cl2)3.4@[(CpBnFeP5)12{CuI}54(MeCN)1.46] ( 2 ) showing a linkage of the scaffold atoms which is beyond the Fullerene topology. Its extended CuI framework reveals an outer diameter of 3.7 nm—a size that has not been reached before using five‐fold symmetric building blocks. Furthermore, 2 shows a remarkable solubility in CH2Cl2, and NMR spectroscopy reveals that the scaffold of the supramolecule remains intact in solution. In addition, a novel 2D polymer [{CpBnFe(η5‐P5)}2{Cu6(μ‐I)2(μ3‐I)4}]n ( 3 ) with an uncommon structural motif was isolated. Its formation can be avoided by using a large excess of CuI in the reaction with 1 . 相似文献
6.
Wenjiang Huang Jinfang Zhang Jianghua Li Chi Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(2):123-126
In the polymeric title compound, [CuI(C10H8N4)]n, the CuI atom is in a four‐coordinated tetrahedral geometry, formed by two I atoms and two pyridine N atoms from two different 4,4′‐(diazenediyl)dipyridine (4,4′‐azpy) ligands. Two μ2‐I atoms link two CuI atoms to form a planar rhomboid [Cu2I2] cluster located on an inversion centre, where the distance between two CuI atoms is 2.7781 (15) Å and the Cu—I bond lengths are 2.6290 (13) and 2.7495 (15) Å. The bridging 4,4′‐azpy ligands connect the [Cu2I2] clusters into a two‐dimensional (2‐D) double‐layered grid‐like network [parallel to the (10) plane], with a (4,4)‐connected topology. Two 2‐D grid‐like networks interweave each other by long 4,4′‐azpy bridging ligands to form a dense 2‐D double‐layered network. To the best of our knowledge, this interwoven 2‐D→2‐D network is observed for the first time in [Cu2I2]–organic compounds. 相似文献
7.
Kiran Kumarvarma Chakrahari Rhone P. Brocha Silalahi Tzu‐Hao Chiu Xiaoping Wang Nadia Azrou Samia Kahlal Yu‐Chiao Liu Ming‐Hsi Chiang Jean‐Yves Saillard C. W. Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(15):4997-5001
The structurally precise Cu‐rich hydride nanoclusters [PdCu14H2(dtc/dtp)6(C≡CPh)6] (dtc: di‐butyldithiocarbamate ( 1 ); dtp: di‐isopropyl dithiophosphate ( 2 )) were synthesized from the reaction of polyhydrido copper clusters [Cu28H15(S2CNnBu2)12]+ or [Cu20H11{S2P(OiPr)2}9] with phenyl acetylene in the presence of Pd(PPh3)2Cl2. Their structures and compositions were determined by single‐crystal X‐ray diffraction and the results supported by ESI‐mass spectrometry. Hydride positions in 1 were confirmed by single‐crystal neutron diffraction. Each hydride is connected to one Pd0 and four CuI atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH2]2? unit and its Cu14 bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded. 相似文献
8.
Ismail Ercan Filiz Ercan Cengiz Arc Orhan Atakol 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(2):m137-m138
A new tetranuclear CuII–HgII–HgII–CuII complex, [Cu2Hg2Cl4(C18H18N2O2)2], has been prepared by means of a copper complex found in the literature. The molecular structure of this complex was determined by X‐ray diffraction and the Cu–Hg–Hg–Cu chain was seen to be non‐linear. The change in magnetic susceptibility with temperature was recorded for this complex and observed to abide by the Curie–Weiss law. The coordination around the HgII ions is square pyramidal. The Cu?Hg bridging distance is 3.5269 (7) Å. 相似文献
9.
Treatment of an acetonitrile solution of CuI with 1, 7‐dithia‐18‐crown‐6 (1, 7‐DT18C6) at 100°C affords the coordination polymer 1[(CuI)2(1, 7‐DT18C6)2] ( 1 ) in which 1, 7‐DT18C6 ligands bridge (CuI)2 rings into double chains. 1D polymers of the type 1[M{(Cu3I4)(1, 7‐DT18C6)}] (M = K, 2 ; M = Cs, 3 ) can be isolated under similar conditions in the presence of respectively KI and CsI. Both contain bridging heptacyclic [Cu6I8]2— units but crystallise in different space groups, namely P1 and C2/m. The cesium cation of 3 is markedly displaced from the best plane through the thiacrown ether donor atoms. Reaction of 1, 7‐DT18C6 with CuSCN in the presence of NaSCN yields 2[{Na(CH3CN)2} {(CuSCN)2(1, 7‐DT18C6)}][Cu(SCN)2] ( 4 ), in which 1[(CuSCN)2] double chains are linked through macrocycles into sheets. Infinite 1[{Cu(SCN)2}—] chains compensate the charge of the Na+ cations. Complex 1 can imbibe 0.90 mol CsNO3 per mol of 1, 7‐DT18C6 pairs. 相似文献
10.
《无机化学与普通化学杂志》2018,644(2):100-108
1‐tert‐Butyl‐1H‐1,2,4‐triazole (tbtr) was found to react with copper(II) chloride or bromide to give the complexes [Cu(tbtr)2X2]n and [Cu(tbtr)4X2] (X = Cl, Br). 1‐tert‐Butyl‐1H‐tetrazole (tbtt) reacts with copper(II) bromide resulting in the formation of the complex [Cu3(tbtt)6Br6]. The obtained crystalline complexes as well as free ligand tbtr were characterized by elemental analysis, IR spectroscopy, thermal and X‐ray analyses. For free ligand tbtr, 1H NMR and 13C NMR spectra were also recorded. In all the complexes, tbtr and tbtt act as monodentate ligands coordinated by CuII cations via the heteroring N4 atoms. The triazole complexes [Cu(tbtr)2Cl2]n and [Cu(tbtr)2Br2]n are isotypic, being 1D coordination polymers, formed at the expense of single halide bridges between neighboring copper(II) cations. The isotypic complexes [Cu(tbtr)4Cl2] and [Cu(tbtr)4Br2] reveal mononuclear centrosymmetric structure, with octahedral coordination of CuII cations. The tetrazole compound [Cu3(tbtt)6Br6] is a linear trinuclear complex, in which neighboring copper(II) cations are linked by single bromide bridges. 相似文献
11.
Wen‐Ge Li You‐Cai Zhang Zuo‐Wei Wang Yi‐Zhi Li He‐Gen Zheng 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(4):m159-m160
The title nest‐shaped cluster, [Cu3WIOS3(C10H8N2)2], has been synthesized by the reaction of (NH4)2[WOS3], CuI and 2,2′‐bipyridine (bipy) in dimethylformamide under a purified nitrogen atmosphere. The cluster has a neutral skeleton containing the bipy ligands, and the central W atom is tetrahedrally coordinated by three S atoms and one O atom. The three Cu atoms are divided into two different kinds. Two Cu atoms adopt distorted tetrahedral geometry, with each Cu atom coordinated by two S atoms and the two N atoms of a bipy ligand. The other Cu atom adopts a trigonal mode surrounded by two S atoms and one I atom. 相似文献
12.
Yong Cui Jiutong Chen Gang Chen Jing Ren Weichao Yu Yitai Qian 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(4):349-351
A novel centrosymmetric chair‐like dimer, bis(2,2′‐bipyridine)‐1κ2N,N′;3κ2N,N′‐tetra‐μ‐chloro‐1:2κ2Cl;2:3κ2Cl;3:4κ2Cl;1:4κ2Cl‐tetracopper(I), [Cu4Cl4(C10H8N2)2], has been solvothermally synthesized and structurally characterized. The complex self‐assembles into a three‐dimensional network via C—H?Cl hydrogen bonds, π–π stacking and weak Cu?Cl electrostatic interactions. 相似文献
13.
Martin M. Kimani Don VanDerveer Julia L. Brumaghim 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(6):m208-m210
In the title compound, catena‐poly[diselanylbis(1,3‐dimethyl‐1H‐imidazol‐3‐ium) [μ3‐chlorido‐tetra‐μ2‐chlorido‐tricuprate(I)]], {(C10H16N4Se2)[Cu3Cl5]}n, the diselenide dication is stabilized by catena‐[Cu3Cl5]2− anions which associate through strong Cu—Cl bonds [average length = 2.3525 (13) Å] to form polymeric chains. The polymeric [Cu3Cl5]2− anion contains crystallographically imposed twofold rotation symmetry, with distorted trigonal‐planar and tetrahedral geometries around the two symmetry‐independent Cu atoms. Likewise, the Se—Se bond of the cation is centered on a twofold rotation axis. 相似文献
14.
A. Sreekanth V. Suni Rohith P. John Munirathinam Nethaji M. R. Prathapachandra Kurup 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(6):m284-m286
The title compound, [Cu2(C17H17N4S)2Cl2], exhibits a dimeric structure related by a centre of symmetry. The monomers are linked to each other by the longest Cu—S apical distance observed to date among CuII square‐pyramidal complexes of N4‐substituted thiosemicarbazones. Each CuII atom deviates from the coordination square plane, which contains the pyridyl and imine N atoms, the thiolate S atom and the Cl− anion, towards the S atom of the adjacent monomer. The dimers pack in a zigzag manner through the crystal. 相似文献
15.
Metal(II) Ion Complexes with 5‐(Pyrazin‐2‐yl)‐2,4‐dihydro‐3H‐1,2,4‐triazole‐3‐thione; Synthesis,Structural Characterization,Acid‐base,and Complexing Properties in Solution 下载免费PDF全文
Aleksander Kufelnicki Jolanta Jaciubek‐Rosińska Marta Sobiesiak Agata Paneth Julia Jezierska Elzbieta Budzisz 《无机化学与普通化学杂志》2017,643(16):1067-1074
The study reports the synthesis of complexes Co(HL)Cl2 ( 1 ), Ni(HL)Cl2 ( 2 ), Cu(HL)Cl2 ( 3 ), and Zn(HL)3Cl2 ( 4 ) with the title ligand, 5‐(pyrazin‐2‐yl)‐1,2,4‐triazole‐5‐thione (HL), and their characterization by elemental analyses, ESI‐MS (m/z), FT‐IR and UV/Vis spectroscopy, as well as EPR in the case of the CuII complex. The comparative analysis of IR spectra of the metal ion complexes with HL and HL alone indicated that the metal ions in 1 , 2 , and 3 are chelated by two nitrogen atoms, N(4) of pyrazine and N(5) of triazole in the thiol tautomeric form, whereas the ZnII ion in 4 is coordinated by the non‐protonated N(2) nitrogen atom of triazole in the thione form. pH potentiometry and UV/Vis spectroscopy were used to examine CoII, NiII, and ZnII complexes in 10/90 (v/v) DMSO/water solution, whereas the CuII complex was examined in 40/60 (v/v) DMSO/water solution. Monodeprotonation of the thione triazole in solution enables the formation of the L:M = 1:1 species with CoII, NiII and ZnII, the 2:1 species with CoII and ZnII, and the 3:1 species with ZnII. A distorted tetrahedral arrangement of the CuII complex was suggested on the basis of EPR and Vis/NIR spectra. 相似文献
16.
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
17.
Dr. Mei Qu Prof. Fu-Qiang Zhang Dian-Hui Wang Prof. Huan Li Dr. Juan-Juan Hou Prof. Xian-Ming Zhang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(16):6569-6574
The only feasible access to non-face-centered cubic (FCC) copper was by physical vapor deposition under high vacuum. Now, non-FCC copper is observed in a series of alkynyl-protected Cu53 nanoclusters (NCs) obtained from solution-phase synthesis. Determined by single-crystal X-ray crystallography, the structures of Cu53(C≡CPhPh)9(dppp)6Cl3(NO3)9 and its two derivatives reveal an ABABC stacking sequence involving 41 Cu atoms. It can be regarded as a mixed FCC and HCP structure, which gives strong evidence that Cu can be arranged in non-FCC lattice at ambient conditions when proper ligands are provided. Characterization methods including X-ray absorption fine structure, XPS, ESI-MS, UV/Vis, Auger spectroscopy, and DFT calculations were carried out. CuII was shown to successively coordinate with introduced ligands and changed to CuI after bonding with phosphine. The following addition of NaBH4 and the aging step further reduced it to the Cu53 NC. 相似文献
18.
Dinuclear Cu(II) complexes based on p‐xylylene‐bridged bis(1,4,7‐triazacyclononane) ligands: Synthesis,characterization, DNA cleavage abilities and evaluation of superoxide dismutase‐ and catalase‐like activities 下载免费PDF全文
Three new dinuclear Cu(II) complexes with the formulas [Cu2(pxdmbtacn)Cl4] ( 1 ), [Cu2(pxdmbtacn)Cl0.7(NO3)1.3(OH)2(H2O)1.3]?6H2O ( 2 ) and [Cu2(pxdiprbtacn)Cl4] ( 3 ) together with one previously reported complex, [Cu2(pxbtacn)Cl4] ( 4 ), were obtained from Cu(II) salts with three p‐xylylene‐bridged bis‐tacn ligands bearing pendant alkyl substituents or without pendant group. Complex 2 was structurally characterized as a centrosymmetric dinuclear molecule with each metal center being coordinated to some labile ligands in addition to one tacn ring. Based on the results of mass spectrometry and UV–visible spectroscopy, complexes 1 and 3 are capable of existing in aqueous solution as dinuclear species but 4 can partially form a dimer of the original dinuclear motif. Complexes 1 , 3 and 4 can all effectively cleave supercoiled DNA oxidatively in the presence of hydrogen peroxide. The superoxide dismutase (SOD) activities of 1 and 3 measured under physiological conditions are comparable to that of the native CuZnSOD enzyme but the enzymatic activity of 4 is about three‐ to fourfold lower. Furthermore, complexes 1 , 3 and 4 demonstrate moderate scavenging effect on hydrogen peroxide and their catalase activities are in the decreasing order of 3 > 1 > 4 . 相似文献
19.
Mao‐Lin Hu Xiao‐Qing Cai Jiu‐Xi Chen 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(9):m403-m405
In the polymeric title compound, [CuCl2(C6H6N4)]n, each CuII ion is five‐coordinated by four basal atoms (two N atoms from a 2,2′‐biimidazole molecule and two Cl− anions) and one axial Cl− anion, in a distorted square‐pyramidal coordination geometry. Cl− anions bridge the {Cu(C6H6N4)Cl} units into one‐dimensional linear chains, which are reinforced by π–π interactions. Adjacent linear chains are linked by N—H⋯Cl hydrogen bonds, resulting in a grid layer. The hydrogen‐bonding pattern can be described in graph‐set notation as C(9)R(9)R(14). This study extends our knowledge of the multifunctional properties of the 2,2′‐biimidazole ligand and of the coordination stereochemistry of copper(II). 相似文献
20.
Dicopper complexes catalyzed coupling/cyclization of 2‐bromobenzoic acids with amidines leading to quinazolinones 下载免费PDF全文
Dicopper(I) complexes {Cu2(bpnp)(CH3CN)4}(PF6)2] ( 2 ), [{Cu2(bpnp)(CH3CN)4}(BAr4F)2] ( 3 ) and [Cu2(bpnp)Cl2] ( 4 ) were prepared from the complexation of [Cu(CH3CN)4](PF6) with 2,7‐bis(2‐pyridyl)‐1,8‐naphthyridine (bpnp) followed by anion metathesis and treatment of chloride sequentially. The X‐ray structural analysis of 4 indicates the molecule to have a twofold axis passing through the Cu2Cl2 core, which has the shape of a butterfly, and that the Cu atom is tetrahedrally coordinated with in a Cl2N2 donor set. In preliminary experiments 2 was found to be an effective catalyst in the coupling/cyclization of 2‐bromobenzoic acids with amidines, providing the corresponding quinazolinones in good yields. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献