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1.
Li-Ying Sun Ting Feng Dr. Rajorshi Das Prof. Dr. F. Ekkehardt Hahn Prof. Dr. Ying-Feng Han 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(41):9764-9770
The development of highly emissive dinuclear AgI or AuI complexes [M2L](PF6)2 (L= 2 a , 2 b ; M=Ag, Au) derived from tetraphenylethylene (TPE)-based tetrabenzimidazolin-2-ylidene ligands is reported. The new complexes exhibit a remarkable fluorescence enhancement compared to their parent benzimidazolium salts. The quantum yield (ΦF) value for salt H4- 2 a (PF6)4 in dilute solution (c=10−5 m ) was found to be less than 1 %, whereas its metal complexes show ΦF values up to 55 % at similar solution concentration. This observation can be attributed to the rigidification of the TPE skeleton upon metalation resulting in a restriction of the intramolecular rotation of the phenyl groups. Functionalization of the complexes [M2 2 b ](PF6)2 (M=Ag, Au) with terminal coumarin groups and subsequent photoirradiation yielded the complexes [M2 3 b ](PF6)2 (M=Ag, Au) bearing a new type of ligand with an unaffected TPE moiety. 相似文献
2.
Yang Li Yuan‐Yuan An Jian‐Zhong Fan Xiao‐Xu Liu Xin Li F. Ekkehardt Hahn Yao‐Yu Wang Ying‐Feng Han 《Angewandte Chemie (International ed. in English)》2020,59(25):10073-10080
A series of supramolecular assemblies of types [Ag8( L )4](PF6)8 and [Ag4( L )2](PF6)4, obtained from the tetraphenylethylene (TPE) bridged tetrakis(1,2,4‐triazolium) salts H4‐L(PF6)4 and AgI ions, is described. The assembly type obtained dependends on the N‐wingtip substituents of H4‐L(PF6)4. Changes in the lengths of the N4‐wingtip substituents enables controlled formation of assemblies with either [Ag4( L )2](PF6)4 or [Ag8( L )4](PF6)8 stoichiometry. The molecular structures of selected [Ag8( L )4](PF6)8 and [Ag4( L )2](PF6)4 assemblies were determined by X‐ray diffraction analyses. While H4‐ L (PF6)4 does not exhibit fluorescence in solution, their tetra‐NHC (NHC=N‐heterocyclic carbene) assemblies do upon NHC–metal coordination. Upon irradiation, all assemblies undergo a light‐induced, supramolecule‐to‐supramolecule structural transformation by an oxidative photocyclization involving phenyl groups of the TPE core, resulting in a significant change of the luminescence properties. 相似文献
3.
A series of dicarbene‐bridged metallacycles [Ag2( 1 )2](PF6)2, [Ag2( 2 )2](BF4)2, [Ag2( 3 )2](PF6)2, [Ag2( 7 )2](BF4)2, [Ag2( 8 )2](BF4)2 and [Ag2( 11 )2](PF6)2 were obtained in high yields via the reactions of 1,2,4‐triazole‐, 1,2,3‐triazole‐ and imidazo[1,5‐a]pyridine‐based ligands with Ag2O in CH3CN. The C=C double bonds in all of the newly synthesized metallacycles went through [2 + 2] photodimerization under UV irradiation condition (λ = 365 nm, T = 298 K) yielding the dinuclear rctt‐cyclobutane‐silver(I) complexes [Ag2( 4 )](PF6)2, [Ag2( 5 )](BF4)2, [Ag2( 6 )](PF6)2, [Ag2( 9 )](BF4)2, [Ag2( 10 )](BF4)2 and [Ag2( 12 )](PF6)2, respectively with quantitative yields. Treatment of the these cyclobutane‐bridged silver(I) complexes with NH4Cl resulted in the exclusive formation of cyclobutane derivatives after removal of the silver(I) metal ions. 相似文献
4.
Yang Li Dr. Yuan-Yuan An Jian-Zhong Fan Xiao-Xu Liu Xin Li Prof. Dr. F. Ekkehardt Hahn Prof. Dr. Yao-Yu Wang Prof. Dr. Ying-Feng Han 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(25):10159-10166
A series of supramolecular assemblies of types [Ag8( L )4](PF6)8 and [Ag4( L )2](PF6)4, obtained from the tetraphenylethylene (TPE) bridged tetrakis(1,2,4-triazolium) salts H4-L(PF6)4 and AgI ions, is described. The assembly type obtained dependends on the N-wingtip substituents of H4-L(PF6)4. Changes in the lengths of the N4-wingtip substituents enables controlled formation of assemblies with either [Ag4( L )2](PF6)4 or [Ag8( L )4](PF6)8 stoichiometry. The molecular structures of selected [Ag8( L )4](PF6)8 and [Ag4( L )2](PF6)4 assemblies were determined by X-ray diffraction analyses. While H4- L (PF6)4 does not exhibit fluorescence in solution, their tetra-NHC (NHC=N-heterocyclic carbene) assemblies do upon NHC–metal coordination. Upon irradiation, all assemblies undergo a light-induced, supramolecule-to-supramolecule structural transformation by an oxidative photocyclization involving phenyl groups of the TPE core, resulting in a significant change of the luminescence properties. 相似文献
5.
Imidazolium salts bearing triazole groups are synthesized via a copper catalyzed click reaction, and the silver, palladium, and platinum complexes of their N‐heterocyclic carbenes are studied. [Ag4(L1)4](PF6)4, [Pd(L1)Cl](PF6), [Pt(L1)Cl](PF6) (L1=3‐((1‐benzyl‐1H‐1,2,3‐triazol‐4‐yl)methyl)‐1‐(pyrimidin‐2‐yl)‐1H‐imidazolylidene), [Pd2(L2)2Cl2](PF6)2, and [Pd(L2)2](PF6)2 (L2=1‐butyl‐3‐((1‐(pyridin‐2‐yl)‐1H‐1,2,3‐triazol‐4‐yl)methyl)imidazolylidene) have been synthesized and fully characterized by NMR, elemental analysis, and X‐ray crystallography. The silver complex [Ag4(L1)4](PF6)4 consists of a Ag4 zigzag chain. The complexes [Pd(L1)Cl](PF6) and [Pt(L1)Cl](PF6), containing a nonsymmetrical NCN ′ pincer ligand, are square planar with a chloride trans to the carbene donor. [Pd2(L2)2Cl2](PF6)2 consists of two palladium centers with CN2Cl coordination mode, whereas the palladium in [Pd(L2)2](PF6)2 is surrounded by two carbene and two triazole groups with two uncoordinated pyridines. The palladium compounds are highly active for Suzuki–Miyaura cross coupling reactions of aryl bromides and 1,1‐dibromo‐1‐alkenes in neat water under an air atmosphere. 相似文献
6.
Le Zhang Rajorshi Das Chang‐Tao Li Yao‐Yu Wang F. Ekkehardt Hahn Kai Hua Li‐Ying Sun Ying‐Feng Han 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(38):13494-13498
Metallosupramolecular poly‐NHC‐metal assemblies were prepared from trigonal hexakis (H6‐ 1 a (PF6)6 and H6‐ 1 b (PF6)6) or nonakis (H9‐ 3 (BF4)9) imidazolium salts and Ag2O. Complexes [Ag6( 1 a )2](PF6)6 and [Ag6( 1 b )2](PF6)6 are built from six Ag+ ions sandwiched between two trigonal hexacarbene ligands with an inner and an outer NHC donor in each of the three ligand arms. The metal atoms are arranged in two triangles. The hexakis‐NHC ligands bear cinnamic ester groups at the outlying NHC donors, used in postsynthetic [2+2] cycloaddition reactions linking two hexakis‐NHC ligands by three cyclobutane units to give complexes [Ag6( 2 a )](PF6)6 and [Ag6( 2 b )](PF6)6 bearing a dodecacarbene ligand. From the related nonakisimidazolium salt H9‐ 3 (BF4)9, complex [Ag9( 4 )](BF4)9 bearing an octadecacarbene ligand was obtained. Removal of the template metals yielded very large, stable, polyimidazolium cations with 12 or 18 internal imidazolium groups. 相似文献
7.
Assembling Quasi‐enantiomeric Octahedral Complexes of Different Metals via Quasi‐racemate Crystallization 下载免费PDF全文
Yanay Popowski Prof. Israel Goldberg Prof. Moshe Kol 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5530-5533
Aiming at a general methodology for binary co‐assembly of complexes of different metals through quasiracemate crystallization, the hexadentate ligand 1 comprised of the chiral bipyrrolidine core and two bipyridine peripheral arms is introduced. Ligand 1 was found to bind in a fully diastereoselective and uniform mode around ZnII, FeII and CdII giving coordinatively inert octahedral “chiral‐at‐metal” complexes with the Δ4Λ2/Λ4Δ2 wrapping mode. Equimolar mixtures of quasienantiomeric pairs of these complexes exhibited a clear tendency to pack as quasiracemates as was revealed from the crystallographic structures of [(R,R)‐ 1 ‐Zn](PF6)2/[(S,S)‐ 1 ‐Fe](PF6)2 and [(R,R)‐ 1 ‐Zn](PF6)2/[(S,S)‐ 1 ‐Cd](PF6)2, in an isomorphous fashion to that of the racemic compound [rac‐ 1 ‐Zn](PF6)2 in space group C2/c. 相似文献
8.
Multi-ligand self-assembly to attain the AgI-N-heterocyclic carbene (NHC)-built hexanuclear organometallic cages of composition [Ag6( 3 a , b )4](PF6)6 from the reaction of benzimidazole-derived tris(azolium) salts [H3- 3 a , b ](PF6)3 with Ag2O was achieved. The molecular structures of the cages were established by X-ray diffraction studies along with NMR and MS analyses. The existence of a single assembly in solution was supported by diffusion-ordered spectroscopy (DOSY) 1H NMR spectra. Further, transmetalation reactions of these self-assembled complexes, [Ag6( 3 a , b )4](PF6)6, with CuI/AuI-ions provided various coinage metal-NHC complexes having diverse molecular compositions, which included the first example of a hexanuclear CuI-dodecacarbene complex, [Cu6( 3 b )4](PF6)6. 相似文献
9.
Ya-Wen Zhang Dr. Rajorshi Das Yang Li Prof. Dr. Yao-Yu Wang Prof. Dr. Ying-Feng Han 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(21):5472-5479
The metal-controlled self-assembly of organometallic molecular cylinders from a series of imidazo[1,5-a]pyridine-based tris-NHC ligands is described in this report. The imidazo[1,5-a]pyridinium salts H3- L (PF6)3 ( L = 4 a – 4 c ) were treated with 1.5 equivalents of Ag2O to yield the trinuclear AgI hexacarbene cages [Ag3( L )2](PF6)3 ( L = 4 a – 4 c ), in which three AgI are sandwiched between the two tricarbene ligands. The silver(I) complexes [Ag3( L )2](PF6)3 underwent a facile transmetalation reaction in the presence of 3 equivalents of [AuCl(tht)] (tht=tetrahydrothiophene) to furnish the trinuclear AuI cylinder-like cages [Au3( L )2](PF6)3 ( L = 4 a – 4 c ) without destruction of the metallosupramolecular structure. The new hexacarbene assemblies feature a large cavity that can easily accommodate a molecule of dimethyl sulfoxide as molecular guest. This is the first study of a unique “host–guest” system containing an organometallic cylinder-like cage derived exclusively from poly-NHC ligands. 相似文献
10.
New hybrid ligands are reported that combine two types of popular donor groups within a single linear scaffold, viz., a central pyrazolate bridge and two appended bis(N‐heterocyclic carbene) units; the ligand strands thus provide two potentially tridentate {NCC} compartments. The pyrazole/tetraimidazolium proligands, [H5L1](PF6)4 and [H5L2](PF6)4 , were synthesized via multi‐step protocols, and the NH prototropy of [H5L1](PF6)4 was examined by variable temperature (VT) NMR spectroscopy, giving solvent dependent activation parameters (ΔH? = 27.6 kJ · mol–1, ΔS? = –125 J · mol–1 · K–1 in [D3]MeCN; ΔH? = 40.4 kJ · mol–1, ΔS? = –86.9 J · mol–1 · K–1 in [D6]DMSO) that are in the range typical for pyrazoles. Reaction of the proligands with Ag2O gave hexametallic complexes [Ag6(L1)2](PF6)4 and [Ag6(L2)2](PF6)4 that involve all six potential donor atoms of the ligands, viz. the four CNHC and two Npz donors, in metal coordination. X‐ray crystallography revealed a chair‐like central {Ag6} deck in both complexes but different arrangements of the ligand strands, which goes along with significantly different AgI ··· AgI distances that indicate more pronounced argentophilic interactions in case of [Ag6(L1)2]4 +. 相似文献
11.
Reversible Mechanical Interlocking of D‐Shaped Molecular Karabiners bearing Coordination‐Bond Loaded Gates: Route to Self‐Assembled [2]Catenanes 下载免费PDF全文
Soumyakanta Prusty Dr. Shobhana Krishnaswamy Sreenivasulu Bandi Dr. Baby Chandrika Dr. Jingwei Luo Prof. Dr. J. Scott McIndoe Prof. Dr. Garry S. Hanan Prof. Dr. Dillip Kumar Chand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15174-15187
Complexation of 1,4‐phenylenebis(methylene) diisonicotinate, L1 , with cis‐protected PdII components, [Pd( L′ )(NO3)2], in an equimolar ratio yielded binuclear complexes, 1 a – d of [Pd2( L′ )2( L1 )2](NO3)4 formulation where L′ stands for ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), and phenanthroline (phen). The combination of 4,4′‐bipyridine, L2 , with the cis‐protected PdII units is known to yield molecular squares, 2 a – d . However, 2 b – d coexist with the corresponding molecular triangles, 3 b – d . Combination of an equivalent each of the ligands L1 and L2 with two equivalents of cis‐protected PdII components in DMSO resulted in the D ‐shaped heteroligated complexes [Pd2( L′ )2( L1 )( L2 )](NO3)4, 4 a – d . Two units of the D ‐shaped complexes interlock, in a concentration dependent fashion, to form the corresponding [2]catenanes [Pd2( L′ )2( L1 )( L2 )]2(NO3)8, 5 a – d under aqueous conditions. Crystal structures of the macrocycle [Pd2(tmeda)2( L1 )( L2 )](PF6)4, 4 b′′ , and the catenane [Pd2(bpy)2( L1 )( L2 )]2(NO3)8, 5 c , provide unequivocal support for the proposed molecular architectures. 相似文献
12.
Shota Yamada Dr. Takeshi Matsumoto Prof. Dr. Ho-Chol Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8268-8278
The oxidation of [MII(3,5-DTBCat)(DTBbpy)] (M=Ni ( [Ni] ), Pd ( [Pd] ), and Pt ( [Pt] ); 3,5-DTBCat=3,5-di-tert-butylcatecholato; DTBbpy=4,4′-di-tert-butyl-2,2′-bipyridine) afforded the dimeric {[NiII(3,5-DTBSQ)(DTBbpy)](PF6)}2 ( {[Ni](PF6)}2 ; 3,5-DTBSQ=3,5-di-tert-butylsemiquinonato) and monomeric semiquinonato (SQ) complexes [MII(3,5-DTBSQ)(DTBbpy)](PF6) (M=Pd ( [Pd](PF6) ) and Pt ( [Pt](PF6) )). The negative solvatochromic properties of the SQ complexes allowed us to estimate the relative order of their dipole moments: [Pd](PF6) > [Pt](PF6) > {[Ni](PF6)}2 . The complexes [Pd](PF6) and [Pt](PF6) adopt monomeric structures and are stable in CH2Cl2 and toluene, whereas they gradually disproportionate at room temperature to [M] and 3,5-di-tert-butylbenzoquinone (3,5-DTBBQ) in polar solvents such as THF, MeOH, EtOH, DMF, or DMSO. The results of spectroscopic studies suggested that the oxidized nickel complex adopts a monomeric structure ( [Ni](PF6) ) in CH2Cl2, but a dimeric structure ( {[Ni](PF6)}2 ) in the other investigated solvents. In polar solvents, {[Ni](PF6)}2 may disproportionate to [Ni] and 3,5-DTBBQ at 323 K, thereby demonstrating a significant solvent- and metal-dependence in temperature. The relative activities of {[Ni](PF6)}2 and [M](PF6) toward disproportionation are related to the electrochemically estimated Kdis values in CH2Cl2 and DMF. The present work demonstrates that solvent polarity and the dipole moments of the SQ complexes promote disproportionation, which can be controlled by a judicious choice of the metal ion, solvent, and temperature. 相似文献
13.
pH‐Controlled Multiple Chiral Inversion That Induces Molecular Dimerization in a Gold(I)–Cobalt(III) Coordination System with L‐Cysteinate 下载免费PDF全文
Pei‐Shan Lee Dr. Asako Igashira‐Kamiyama Dr. Naoto Kuwamura Dr. Nobuto Yoshinari Prof. Takumi Konno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6646-6649
Herein, a unique coordination system that exhibits multiple chiral inversions and molecular dimerization in response to a subtle pH change is reported. Treatment of (Δ)2‐H3[Au3Co2(L ‐cys)6] (H3[ 1 a ]) with [Co3(aet)6](NO3)3 (aet=2‐aminoethanethiolate) in water at pH 7 gave a 1:1 complex salt of [Co3(aet)6]3+ and [ 1 a ]3?, retaining the AuI3CoIII2 structure and chiral configurations of [ 1 a ]3?. Similar treatment at pH 9 led to not only the inversion of all of the chiral CoIII and S centers but also the dimerization of [ 1 a ]3?, giving a 2:1 complex salt of [Co3(aet)6]3+ and (Λ)4(R)12‐[Au6Co4(L ‐cys)12]6? ([ 2 ]6?). When dissociated from [Co3(aet)6]3+ in solution, [ 2 ]6? was converted to (Λ)2(R)6‐[Au3Co2(L ‐cys)6]3? ([ 1 b ]3?) with retention of the chiral configurations. 相似文献
14.
An Extremely Porous Hydrogen‐Bonded Framework Composed of d‐Penicillaminato CoIII2AuI3 Complex Anions and Aqua Cobalt(II) Cations: Formation and Stepwise Structural Transformation 下载免费PDF全文
Sireenart Surinwong Dr. Nobuto Yoshinari Dr. Bunlawee Yotnoi Prof. Takumi Konno 《化学:亚洲杂志》2016,11(4):486-490
A unique example of a hydrogen‐bonded ionic solid with a porosity of 80 %, [Co(H2O)6]3[Co2Au3(d ‐pen‐N,S)6]2 ( 1 ; d ‐H2pen=d ‐penicillamine), composed of [Co(H2O)6]2+ cations and [Co2Au3(d ‐pen‐N,S)6]3? anions, is reported. Solid 1 was kinetically produced and was then transformed stepwise into two more thermodynamically stable solids with lower porosities, [Co(H2O)4][Co(H2O)6]2[Co2Au3(d ‐pen‐N,S)6]2 ( 2 ) and [Co(H2O)4]3[Co2Au3(d ‐pen‐N,S)6]2 ( 3 ), through the coordination of the free carboxylate groups in [Co2Au3(d ‐pen‐N,S)6]3? to CoII centers. Solids 1 – 3 were structurally characterized, and the selective adsorption of small molecules into their pores was investigated. 相似文献
15.
Heterodinuclear Ruthenium(II) Complexes of the Bridging Ligand 1,6,7,12‐Tetraazaperylene with Iron(II), Cobalt(II), Nickel(II), as well as Palladium(II) and Platinum(II) 下载免费PDF全文
Thomas Brietzke Alexandra Kelling Uwe Schilde Wulfhard Mickler Hans‐Jürgen Holdt 《无机化学与普通化学杂志》2016,642(1):8-13
The first heterodinuclear ruthenium(II) complexes of the 1,6,7,12‐tetraazaperylene (tape) bridging ligand with iron(II), cobalt(II), and nickel(II) were synthesized and characterized. The metal coordination sphere in this complexes is filled by the tetradentate N,N′‐dimethyl‐2,11‐diaza[3.3](2,6)‐pyridinophane (L‐N4Me2) ligand, yielding complexes of the general formula [(L‐N4Me2)Ru(µ‐tape)M(L‐N4Me2)](ClO4)2(PF6)2 with M = Fe {[ 2 ](ClO4)2(PF6)2}, Co {[ 3 ](ClO4)2(PF6)2}, and Ni {[ 4 ](ClO4)2(PF6)2}. Furthermore, the heterodinuclear tape ruthenium(II) complexes with palladium(II)‐ and platinum(II)‐dichloride [(bpy)2Ru(μ‐tape)PdCl2](PF6)2 {[ 5 ](PF6)2} and [(dmbpy)2Ru(μ‐tape)PtCl2](PF6)2 {[ 6 ](PF6)2}, respectively were also prepared. The molecular structures of the complex cations [ 2 ]4+ and [ 4 ]4+ were discussed on the basis of the X‐ray structures of [ 2 ](ClO4)4 · MeCN and [ 4 ](ClO4)4 · MeCN. The electrochemical behavior and the UV/Vis absorption spectra of the heterodinuclear tape ruthenium(II) complexes were explored and compared with the data of the analogous mono‐ and homodinuclear ruthenium(II) complexes of the tape bridging ligand. 相似文献
16.
《中国化学快报》2022,33(10):4567-4571
A trefoil-like two-dimensional (2D) C3v symmetric organic [12]-imidazolium cation H12–2(PF6)12 featuring three [4]-imidazolium macrocycles was synthesized in three steps. The reaction of a dodecakis H12–1(PF6)12 imidazolium salt with Ag2O resulted in the formation of a hexanuclear AgI dodecacarbene assembly [Ag6(1)](PF6)6. Upon UV irradiation, the photodimerization of the cinnamic ester pendants of [Ag6(1)](PF6)6 led to the generation of a trefoil-like complex [Ag6(2)](PF6)6 containing three closed metallacycles. Removal of metal ions allowed for the synthesis of the target molecule. All complexes were fully characterized by NMR spectroscopy (1H, 13C{1H} and 2D NMR) and high-resolution electrospray ionization mass spectrometry (HR-ESI-MS). 相似文献
17.
Ya-Wen Zhang Dr. Ye Lu Dr. Li-Ying Sun Dr. Patrick D. Dutschke Ming-Ming Gan Le Zhang Dr. Alexander Hepp Ying-Feng Han Prof. Dr. F. Ekkehardt Hahn 《Angewandte Chemie (International ed. in English)》2023,62(50):e202312323
A series of [2]catenanes has been prepared from di-NHC building blocks by utilizing solvophobic effects and/or π⋅⋅⋅π stacking interactions. The dinickel naphthobiscarbene complex syn-[ 1 ] and the kinked biphenyl-bridged bipyridyl ligand L2 yield the [2]catenane [ 2-IL ](OTf)4 by self-assembly. Solvophobic effects are pivotal for the formation of the interlocked species. Substitution of the biphenyl-linker in L2 for a pyromellitic diimide group gave ligand L3 , which yielded in combination with syn-[ 1 ] the [2]catenane [ 3-IL ](OTf)4. This assembly exhibits enhanced stability in diluted solution, aided by additional π⋅⋅⋅π stacking interactions. The π⋅⋅⋅π stacking was augmented by the introduction of a pyrene bridge between two NHC donors in ligand L4 . Di-NHC precursor H2- L4 (PF6)2 reacts with Ag2O to give the [Ag2 L4 2]2 [2]catenane [ 4-IL ](PF6)4, which shows strong π⋅⋅⋅π stacking interactions between the pyrene groups. This assembly was readily converted into the [Au2 L4 2]2 gold species [ 5-IL ](PF6)4, which exhibits exceptional stability based on the strong π⋅⋅⋅π stacking interactions and the enhanced stability of the Au-CNHC bonds. 相似文献
18.
Pedro Aguirre Sergio A. Moya Renato Sariego Hubert Le Bozec Alvaro J. Pardey 《应用有机金属化学》2002,16(10):597-600
Ruthenium complexes of the type [RuL(CO)2Cl2], [RuL2Cl2], [RuL2(CO)(H2O)](PF6)2, [RuL2Cl]2(PF6)2, [RuL2(CO)Cl](PF6), and [RuL2(CO3)]·3H2O (where L is a bipyridine or phenanthroline derivative) dissolved in aqueous 2‐ethoxyethanol, and in a basic medium of KOH, triethylamine, or trimethylamine, catalyze the water‐gas shift reaction under mild conditions (PCO = 0.9 atm at 100 °C). Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
19.
《化学:亚洲杂志》2018,13(15):1906-1910
A unique example of a ring‐to‐cage structural conversion in a multinuclear gold(I) coordination system with d ‐penicillamine (d ‐H2pen) is reported. The reaction of [Au2Cl2(dppe)] (dppe=1,2‐bis(diphenylphosphino)ethane) with d ‐H2pen in a 1:1 ratio gave [Au4(dppe)2(d ‐pen)2] ([ 1 ]), in which two [Au2(dppe)]2+ units are linked by two d ‐pen S atoms in a cyclic form so as to have two bidentate‐N,O coordination arms. The subsequent reaction of [ 1 ] with Cu(OTf)2 afforded [Au4Cu(dppe)2(d ‐pen)2]2+ ([ 2 ]2+), in which a CuII ion is chelated by the two coordination arms in [ 1 ] to form an AuI4CuII bicyclic metallocage. A similar reaction using Cu(NO3)2 was accompanied by the ring expansion of [ 1 ] to [Au8(dppe)4(d ‐pen)4], leading to the production of [Au8Cu2(dppe)4(d ‐pen)4]4+ ([ 3 ]4+). In [ 3 ]4+, two CuII ions are each chelated by the two coordination arms to form an AuI8CuII2 tricyclic metallocage, accommodating a nitrate ion. The use of Ni(NO3)2 or Ni(OAc)2 instead of Cu(NO3)2 commonly gave a tricyclic metallocage of [Au8Ni2(dppe)4(d ‐pen)4]4+ ([ 4 ]4+), but a water molecule was accommodated inside the AuI8NiII2 metallocage. 相似文献
20.
The reaction of [Pt(CH2COMe)(Ph)(cod)] (cod=1,5‐cyclooctadiene) with (ArCH2NH2CH2‐C6H4COOH)+(PF6)? (Ar=4‐tBuC6H4 or 9‐anthryl) in the presence of cyclic oligoethers such as dibenzo[24]crown‐8 (DB24C8) and dicyclohexano[24]crown‐8 (DC24C8) produces {(ce)[ArCH2NH2CH2C6H4COOPt(Ph)(cod)]}+(PF6)? (ce=DB24C8 or DC24C8, Ar=4‐tBuC6H4 or 9‐anthryl) with interlocked structures. FABMS and NMR spectra of a solution of these compounds indicate that the Pt complexes with a secondary ammonium group and DB24C8 (or DC24C8) make up the axis and cyclic components, respectively. Temperature‐dependent 1H NMR spectra of a solution of {(DB24C8)[4‐tBuC6H4CH2NH2CH2‐C6H4COOPt(Ph)(cod)]}+(PF6)? ({(DB24C8)[ 4 ‐H]}+(PF6)?) show equilibration with free DB24C8 and the axis component. The addition of DB24C8 to a solution of {(DC24C8)[ 4 ‐H]}+(PF6)? causes partial exchange of the macrocyclic component of the interlocked molecules, giving a mixture of {(DC24C8)[ 4 ‐H]}+(PF6)?, {(DB24C8)[ 4 ‐H]}+(PF6)?, and free macrocyclic compounds. The reaction of 3,5‐Me2C6H3COCl with {(DB24C8)[ 4 ‐H]}+(PF6)? affords the organic rotaxane {(DB24C8)(4‐tBuC6H4CH2NH2CH2‐C6H4COOCOC6H3Me2‐3,5)}+(PF6)? through C? O bond formation between the aroyl group and the carboxylate ligand of the axis component. The addition of 2,2′‐bipyridine (bpy) to a solution of {(DB24C8)[ 4 ‐H]}+(PF6)? induces the degradation of the interlocked structure to form a complex with trigonal bipyramidal coordination, [Pt(Ph)(bpy)(cod)]+(PF6)?, whereas the reaction of bpy with [Pt(OCOC6H4Me‐4)(Ph)(cod)] produces the square‐planar complex [Pt(OCOC6H4Me‐4)(Ph)(bpy)]. 相似文献