共查询到20条相似文献,搜索用时 15 毫秒
1.
Hendrik Leopold Dr. Mario Tenne Dr. Alexander Tronnier Dr. Stefan Metz Dr. Ingo Münster Dr. Gerhard Wagenblast Prof. Dr. Thomas Strassner 《Angewandte Chemie (International ed. in English)》2016,55(51):15779-15782
Binuclear C^C* cyclometalated NHC platinum(II) compounds with bridging amidinate ligands were synthesized to evaluate their photophysical properties. Their three‐dimensional structures were determined by a combination of 2D NMR experiments, mass spectrometry, DFT calculations, and solid‐state structure analysis. The bridging amidinate ligands enforce short distances between the platinum centers of the two cyclometalated structures, which gives rise to extraordinary photophysical properties. 相似文献
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Dr. Ester Rossi Dr. Alessia Colombo Dr. Claudia Dragonetti Dr. Stefania Righetto Prof. Dr. Dominique Roberto Prof. Dr. Renato Ugo Dr. Adriana Valore Prof. Dr. J. A. Gareth Williams Dr. Maria Grazia Lobello Dr. Filippo De Angelis Dr. Simona Fantacci Prof. Dr. Isabelle Ledoux‐Rak Dr. Anu Singh Prof. Dr. Joseph Zyss 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(30):9875-9883
Appropriate functionalization of the cyclometalated ligand, L , and the choice of the ancillary ligand, X, allows the dipolar second‐order nonlinear optical response of luminescent [Pt L X] complexes—in which L is an N^C^N‐coordinated 1,3‐di(2‐pyridyl)benzene ligand and X is a monodentate halide or acetylide ligand—to be controlled. The complementary use of electric‐field‐induced second‐harmonic (EFISH) generation and harmonic light scattering (HLS) measurements demonstrates how the quadratic hyperpolarizability of this appealing family of multifunctional chromophores, characterized by a good transparency throughout much of the visible region, is dominated by an octupolar contribution. 相似文献
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Dr. Simone Alidori Dominikus Heift Dr. Gustavo Santiso‐Quinones Dr. Zoltán Benkő Prof. Dr. Hansjörg Grützmacher Dr. Maria Caporali Dr. Luca Gonsalvi Dr. Andrea Rossin Dr. Maurizio Peruzzini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(46):14805-14811
The terminal rhenium(I) phosphaethynolate complex [Re(PCO)(CO)2(triphos)] has been prepared in a salt metathesis reaction from Na(OCP) and [Re(OTf)(CO)2(triphos)]. The analogous isocyanato complex [Re(NCO)(CO)2(triphos)] has been likewise prepared for comparison. The structure of both complexes was elucidated by X‐ray diffraction studies. While the isocyanato complex is linear, the phosphaethynolate complex is strongly bent around the pnictogen center. Computations including natural bond orbital (NBO) theory, natural resonance theory (NRT), and natural population analysis (NPA) indicate that the isocyanato complex can be viewed as a classic Werner‐type complex, that is, with an electrostatic interaction between the ReI and the NCO group. The phosphaethynolate complex [Re(P?C?O)(CO)2(triphos)] is best described as a metallaphosphaketene with a ReI–phosphorus bond of highly covalent character. 相似文献
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Barbara Di Credico Dipl.‐Chem. Fabrizia Fabrizi de Biani Dr. Luca Gonsalvi Dr. Annalisa Guerri Dr. Andrea Ienco Dr. Franco Laschi Prof. Dr. Maurizio Peruzzini Dr. Gianna Reginato Dr. Andrea Rossin Dr. Piero Zanello Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):11985-11998
The reaction of [CpRuCl(PPh3)2] (Cp=cyclopentadienyl) and [CpRuCl(dppe)] (dppe=Ph2PCH2CH2PPh2) with bis‐ and tris‐phosphine ligands 1,4‐(Ph2PC≡C)2C6H4 ( 1 ) and 1,3,5‐(Ph2PC≡C)3C6H3 ( 2 ), prepared by Ni‐catalysed cross‐coupling reactions between terminal alkynes and diphenylchlorophosphine, has been investigated. Using metal‐directed self‐assembly methodologies, two linear bimetallic complexes, [{CpRuCl(PPh3)}2(μ‐dppab)] ( 3 ) and [{CpRu(dppe)}2(μ‐dppab)](PF6)2 ( 4 ), and the mononuclear complex [CpRuCl(PPh3)(η1‐dppab)] ( 6 ), which contains a “dangling arm” ligand, were prepared (dppab=1,4‐bis[(diphenylphosphino)ethynyl]benzene). Moreover, by using the triphosphine 1,3,5‐tris[(diphenylphosphino)ethynyl]benzene (tppab), the trimetallic [{CpRuCl(PPh3)}3(μ3‐tppab)] ( 5 ) species was synthesised, which is the first example of a chiral‐at‐ruthenium complex containing three different stereogenic centres. Besides these open‐chain complexes, the neutral cyclic species [{CpRuCl(μ‐dppab)}2] ( 7 ) was also obtained under different experimental conditions. The coordination chemistry of such systems towards supramolecular assemblies was tested by reaction of the bimetallic precursor 3 with additional equivalents of ligand 2 . Two rigid macrocycles based on cis coordination of dppab to [CpRu(PPh3)] were obtained, that is, the dinuclear complex [{CpRu(PPh3)(μ‐dppab)}2](PF6)2 ( 8 ) and the tetranuclear square [{CpRu(PPh3)(μ‐dppab)}4](PF6)4 ( 9 ). The solid‐state structures of 7 and 8 have been determined by X‐ray diffraction analysis and show a different arrangement of the two parallel dppab ligands. All compounds were characterised by various methods including ESIMS, electrochemistry and by X‐band ESR spectroscopy in the case of the electrogenerated paramagnetic species. 相似文献
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Glenna So Ming Tong Dr. Yuen‐Chi Law Dr. Steven C. F. Kui Dr. Nianyong Zhu Dr. King Hong Leung Dr. David Lee Phillips Prof. Chi‐Ming Che Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(22):6540-6554
The complexes [Pt(tBu3tpy){C?C(C6H4C?C)n?1R}]+ (n=1: R=alkyl and aryl (Ar); n=1–3: R=phenyl (Ph) or Ph‐N(CH3)2‐4; n=1 and 2, R=Ph‐NH2‐4; tBu3tpy=4,4’,4’’‐tri‐tert‐butyl‐2,2’:6’,2’’‐terpyridine) and [Pt(Cl3tpy)(C?CR)]+ (R=tert‐butyl (tBu), Ph, 9,9’‐dibutylfluorene, 9,9’‐dibutyl‐7‐dimethyl‐amine‐fluorene; Cl3tpy=4,4’,4’’‐trichloro‐2,2’:6’,2’’‐terpyridine) were prepared. The effects of substituent(s) on the terpyridine (tpy) and acetylide ligands and chain length of arylacetylide ligands on the absorption and emission spectra were examined. Resonance Raman (RR) spectra of [Pt(tBu3tpy)(C?CR)]+ (R=n‐butyl, Ph, and C6H4‐OCH3‐4) obtained in acetonitrile at 298 K reveal that the structural distortion of the C?C bond in the electronic excited state obtained by 502.9 nm excitation is substantially larger than that obtained by 416 nm excitation. Density functional theory (DFT) and time‐dependent DFT (TDDFT) calculations on [Pt(H3tpy)(C?CR)]+ (R= n‐propyl (nPr), 2‐pyridyl (Py)), [Pt(H3tpy){C?C(C6H4C?C)n?1Ph}]+ (n=1–3), and [Pt(H3tpy){C?C(C6H4C?C)n?1C6H4‐N(CH3)2‐4}]+/+H+ (n=1–3; H3tpy=nonsubstituted terpyridine) at two different conformations were performed, namely, with the phenyl rings of the arylacetylide ligands coplanar (“cop”) with and perpendicular (“per”) to the H3tpy ligand. Combining the experimental data and calculated results, the two lowest energy absorption peak maxima, λ1 and λ2, of [Pt(Y3tpy)(C?CR)]+ (Y=tBu or Cl, R=aryl) are attributed to 1[π(C?CR)→π*(Y3tpy)] in the “cop” conformation and mixed 1[dπ(Pt)→π*(Y3tpy)]/1[π(C?CR)→π*(Y3tpy)] transitions in the “per” conformation. The lowest energy absorption peak λ1 for [Pt(tBu3tpy){C?C(C6H4C?C)n?1C6H4‐H‐4}]+ (n=1–3) shows a redshift with increasing chain length. However, for [Pt(tBu3tpy){C?C(C6H4C?C)n?1C6H4‐N(CH3)2‐4}]+ (n=1–3), λ1 shows a blueshift with increasing chain length n, but shows a redshift after the addition of acid. The emissions of [Pt(Y3tpy)(C?CR)]+ (Y=tBu or Cl) at 524–642 nm measured in dichloromethane at 298 K are assigned to the 3[π(C?CAr)→π*(Y3tpy)] excited states and mixed 3[dπ(Pt)→π*(Y3tpy)]/3[π(C?C)→π*(Y3tpy)] excited states for R=aryl and alkyl groups, respectively. [Pt(tBu3tpy){C?C(C6H4C?C)n?1C6H4‐N(CH3)2‐4}]+ (n=1 and 2) are nonemissive, and this is attributed to the small energy gap between the singlet ground state (S0) and the lowest triplet excited state (T1). 相似文献
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Lucia Ambrosio M. Carla Aragoni Dr. Massimiliano Arca Dr. Francesco A. Devillanova Prof. Michael B. Hursthouse Prof. Dr. Susanne L. Huth Dr. Francesco Isaia Prof. Vito Lippolis Prof. Dr. Annalisa Mancini Dr. Anna Pintus Dr. 《化学:亚洲杂志》2010,5(6):1395-1406
The tetrabutylammonium (TBA+) salts of square‐planar monoanionic gold complexes of the unsymmetrically substituted Ar,H‐edt2? 1,2‐dithiolene ligands (Ar,H‐edt2?=arylethylene‐1,2‐dithiolato; Ar=phenyl ( 1 ?), 2‐naphthyl ( 2 ?), and 1‐pyrenyl ( 3 ?)) were synthesized and characterized by spectroscopic and electrochemical methods and the corresponding neutral species ( 1 , 2 , and 3 , respectively) were obtained in CH2Cl2 solution at room temperature by diiodine oxidation. The single‐crystal X‐ray diffraction structural data collected for (TBA+)( 2 ?), supported by DFT theoretical calculations, are consistent with the ene‐1,2‐dithiolate form of the ligand and the AuIII oxidation state. All complexes feature intense near‐IR absorptions (at about 1.5 μm) in their neutral states and Vis‐emitting properties in the 400–550 nm range, the energy of which is controlled by the charge of the complex in the case of the 3 ?/ 3 couple. The spectroscopic and electrochemical features of 1 x? and 2 x? (x=0, 1), both in their cis and trans conformations, were investigated by means of DFT and time‐dependent (TD) DFT calculations. 相似文献
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Adrien T. Normand Dr. Mikhail S. Nechaev Dr. Kingsley J. Cavell Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(29):7063-7073
A detailed experimental and DFT study (PBE level) of the reaction of [Pd(η3‐C3H5)(tmiy)(PR3)]BF4 (tmiy=tetramethylimidazolin‐2‐ylidene, PR3=phosphane), precursors to monoligated Pd0 species, with aryl electrophiles yielding 2‐arylimidazolium salt is reported. Experiments establish that an autocatalytic ligand transfer mechanism is preferred over PdIV and σ‐bond metathesis pathways, and that transmetalation is the rate‐determining step. Calculations indicate that the key step involves the concerted exchange of NHC and iodo ligands between two different PdII complexes. This is corroborated by experimental results showing the slower reaction of complexes containing the bulkier dipdmiy (dipdmiy = diisopropyldimethylimidazolin‐2‐ylidene). 相似文献
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Ishii A Kashiura S Hayashi Y Weigand W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(15):4326-4333
Reaction of the title bicyclic disulfide 16 with [(Ph3P)2Pt(eta2-C2H4)] (2) yielded the corresponding (dithiolato)platinum(II) complex 17 by oxidative addition. The initial product 17 isomerized at room temperature in a [1,5]-sulfur rearrangement to give another (dithiolato)platinum(II) complex 18 in high isolated yield. Oxidation reactions of 18 with dimethyldioxirane (DMD) provided (sulfenato-thiolato)platinum(II) 23, (sulfinato-thiolato)platinum(II) 24, (sulfenato-sulfinato)platinum(II) 25, and (disulfinato)platinum(II) 26 complexes, the structures of which were elucidated by NMR spectroscopy and X-ray crystallography. The oxidation process took place regioselectively in the first step and chemoselectively in the second. The selectivities are discussed. 相似文献
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Dr. Mari Toyama Takako Takizawa Itaru Morita Prof. Noriharu Nagao Dr. Yusuke Kuramochi Prof. Hitoshi Ishida 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16582-16590
Two isomers of heteroleptic bis(bidentate) ruthenium(II) complexes with dimethyl sulfoxide (dmso) and chloride ligands, trans(Cl,Nbpy)- and trans(Cl,NHdpa)-[Ru(bpy)Cl(dmso-S)(Hdpa)]+ (bpy: 2,2′-bipyridine; Hdpa: di-2-pyridylamine), are synthesized. This is the first report on the selective synthesis of a pair of isomers of cis-[Ru(L)(L′)XY]n+ (L≠L′: bidentate ligands; X≠Y: monodentate ligands). The structures of the ruthenium(II) complexes are clarified by means of X-ray crystallography, and the signals in the 1H NMR spectra are assigned based on 1H–1H COSY spectra. The colors of the two isomers are clearly different in both the solid state and solution: the trans(Cl,Nbpy) isomer has a deep red color, whereas the trans(Cl,NHdpa) isomer is yellow. Although both complexes have intense absorption bands at λ≈440–450 nm, only the trans(Cl,Nbpy) isomer has a shoulder band at λ≈550 nm. DFT calculations indicate that the LUMOs of both isomers are the π* orbitals in the bpy ligand, and that the LUMO level of the trans(Cl,Nbpy) isomer is lower than that of the trans(Cl,NHdpa) isomer due to the trans effect of the Cl ligand; thus resulting in the appearance of the shoulder band. The HOMO levels are almost the same in both isomers. The energy levels are experimentally supported by cyclic voltammograms, in which these isomers have different reduction potentials and similar oxidation potentials. 相似文献
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Prof. Dr. Wen‐Kui Dong Yin‐Xia Sun Guo‐Hua Liu Li Li Xiu‐Yan Dong Xiong‐Hou Gao 《无机化学与普通化学杂志》2012,638(9):1370-1377
Two nickel(II) complexes, namely {[NiL(MeOH)(μ‐OAc)]2Ni} · 2CH2Cl2 · 2MeOH ( 1 ) and {[NiL(EtOH)(μ‐OAc)]2Ni} · 2EtOH ( 2 ) {H2L = 5, 5′‐dimethoxy‐2, 2′‐[(ethylene)dioxybis(nitrilomethylidyne)]diphenol}, were synthesized and structurally characterized. Two trinuclear NiII complexes are both hexacoordinate around the central NiII atoms, showing octahedral coordination arrangements, and each complex comprises three divalent NiII atoms, two deprotonated L2– ligands, in which four μ‐phenoxo oxygen atoms forming two [NiL(X)] (X = MeOH or EtOH) units, and coordinated and non‐coordinated solvent molecules. Complex 1 exhibits a 2D supramolecular network through intermolecular O–H ··· O, C–H ··· O and C–H ··· π interactions, whereas complex 2 forms an infinite 1D chain by intermolecular C–H ··· O hydrogen bonding interactions. 相似文献
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Guillaume Berthon‐Gelloz Dr. Bas de Bruin Dr. Bernard Tinant Prof. István E. Markó Prof. 《Angewandte Chemie (International ed. in English)》2009,48(17):3161-3164
Y not? A unique, three‐coordinate Y‐shaped bis(silyl)platinum(II) complex was isolated and characterized (see structure; C light gray, N blue, Si pink, Pt dark gray). DFT studies on a model system shed light on the nature of this unusual coordination mode for platinum(II).
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Min‐Shiun Chao Horng‐Hwa Lu Ming‐Liao Tsai Tsung‐Hsuan Hsieh Chien‐Min Lin 《中国化学会会志》2009,56(5):916-922
The self‐assembly of Co(II) with two diaminodiamide ligands, 4,7‐diazadecanediamide and 4,8‐diazaundecanediamide, gave two different crystals, [(C8H18N4O2)Co(OH)2Co(C8H18N4O2)]Cl2 ( 1 ) [Co(C9H20N4O2)(Cl)(H2O)]·Cl·2H2O ( 2 ). Structures of 1 and 2 were characterized by single‐crystal X‐ray diffraction analysis. Structural data for 1 shows a novel type of binuclear complex with distorted octahederal coordination geometry around the Co atoms through the hydroxo bridges. By using inter‐connector N‐H···N hydrogen bonding interactions as building forces, each cationic moiety [(C8H18N4O2)Co(OH)2Co(C8H18N4O2)]2+ is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chain‐like structure. The chains are further connected into a 2D layer in a (4,4)‐topology via N‐H···Clfree hydrogen‐bonding interactions. Structural data for 2 indicate that the cobalt atom adopts a six‐coordinated N2O4 environment, giving a distorted octahedral geometry, where two N‐ and two O‐donor sets of ligand located at equatorial positions and one water and one chloride occupied at axial positions. Through NH···Cl‐Co and OH···Cl‐Co contacts, each cationic moiety [Co(C9H20N4O2)(Cl)(H2O)]+ in 2 is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chainlike structure. Thus, the crystal‐engineering approach has proved successful in the solid‐state packing due to steric strain effect of the diaminodiamide ligand. 相似文献
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Das A Dash C Yousufuddin M Celik MA Frenking G Dias HV 《Angewandte Chemie (International ed. in English)》2012,51(16):3940-3943
Golden trefoils: Tris(alkyne)gold complex [(coct)(3)Au][SbF(6)] (see picture; 1-SbF(6)) can be synthesized from cyclooctyne (coct) and AuSbF(6) generated in situ. Treatment of AuCl with cyclooctyne led to the bis(alkyne)gold complex [Au(coct)(2)Cl] (2). DFT analysis indicates that the cyclooctyne ligands are net electron donors in 1 but overall electron acceptors in 2. AuSbF(6) is shown to mediate [2+2+2] cycloaddition reactions of alkynes. 相似文献