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Synthesis,Characterization, and Theoretical Investigation of Two‐Coordinate Palladium(0) and Platinum(0) Complexes Utilizing π‐Accepting Carbenes 下载免费PDF全文
Dr. Sudipta Roy Dr. Kartik Chandra Mondal Dipl.‐Chem. Jann Meyer Dipl.‐Chem. Benedikt Niepötter Christian Köhler Dr. Regine Herbst‐Irmer Prof. Dr. Dietmar Stalke Dr. Birger Dittrich Dr. Diego M. Andrada Prof. Dr. Gernot Frenking Prof. Dr. Herbert W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(26):9312-9318
An elegant general synthesis route for the preparation of two coordinate palladium(0) and platinum(0) complexes was developed by reacting commercially available tetrakis(triphenylphosphine)palladium/platinum with π‐accepting cyclic alkyl(amino) carbenes (cAACs). The complexes are characterized by NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray diffraction. The palladium complexes exhibit sharp color changes (crystallochromism) from dark maroon to bright green if the C‐Pd‐C bond angle is sharpened by approximately 6°, which is chemically feasible by elimination of one lattice THF solvent molecule. The analogous dark orange‐colored platinum complexes are more rigid and thus do not show this phenomenon. Additionally, [(cAAC)2Pd/Pt] complexes can be quasi‐reversibly oxidized to their corresponding [(cAAC)2Pd/Pt]+ cations, as evidenced by cyclic voltammetry measurements. The bonding and stability are studied by theoretical calculations. 相似文献
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Inside Cover: Synthesis,Characterization, and Theoretical Investigation of Two‐Coordinate Palladium(0) and Platinum(0) Complexes Utilizing π‐Accepting Carbenes (Chem. Eur. J. 26/2015) 下载免费PDF全文
Dr. Sudipta Roy Dr. Kartik Chandra Mondal Dipl.‐Chem. Jann Meyer Dipl.‐Chem. Benedikt Niepötter Christian Köhler Dr. Regine Herbst‐Irmer Prof. Dr. Dietmar Stalke Dr. Birger Dittrich Dr. Diego M. Andrada Prof. Dr. Gernot Frenking Prof. Dr. Herbert W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(26):9266-9266
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Dr. Kartik Chandra Mondal Dr. Sudipta Roy Dr. Susmita De Dr. Pattiyil Parameswaran Dr. Birger Dittrich Dr. Fabian Ehret Prof. Dr. Wolfgang Kaim Prof. Dr. Herbert W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(37):11646-11649
Compound (Me2‐cAAC:)2Co0 ( 2 ; Me2‐cAAC:=cyclic (alkyl) amino carbene; :C(CH2)(CMe2)2N‐2,6‐iPr2C6H3) was synthesized by the reduction of the precursor (Me2‐cAAC:)2CoICl ( 1 ) with KC8 in THF. The cyclic voltammogram of 1 exhibited one‐electron reduction, which suggests that synthesis of a bent 2‐metallaallene ( 2 ) from 1 should be possible. Compound 2 contains one cobalt atom in the formal oxidation state zero, which is stabilized by two Me2‐cAAC: ligands. Bond lengths from X‐ray diffraction are 1.871(2) and 1.877(2) Å with a C‐Co‐C bond angle of 170.12(8)°. The EPR spectrum of 2 exhibited a broad resonance attributed to the unique quasi‐linear structure, which favors near degeneracy and gives rise to very rapid relaxation conditions. The cAAC?Co bond in 2 can be considered as a typical Dewar–Chatt–Duncanson type of bonding, which in turn retains 2.5 electron pairs on the Co atom as nonbonding electrons. 相似文献
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Ryota Sakamoto Dr. Shoko Kume Dr. Manabu Sugimoto Prof. Dr. Hiroshi Nishihara Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(6):1429-1439
Azobenzene derivatives modified with dithiolato‐bipyridine platinum(II) complexes were synthesized, revealing their highly extended photoresponses to the long wavelength region as well as unique photocontrollable tristability. The absorptions of trans‐ 1 and trans‐ 2 with one azobenzene group on the dithiolene and bipyridine ligands, respectively, cover the range from 300 to 700 nm. These absorptions are ascribed, by means of time‐dependent (TD)DFT calculations, to transitions from dithiolene(π) to bipyridine(π*), namely, interligand charge transfer (CT), π–π*, and n–π* transitions of the azobenzene unit, and π–π* transitions of the bipyridine ligand. In addition, only trans‐ 1 shows distinctive electronic bands, assignable to transitions from the dithiolene(π) to azobenzene(π*), defined as intraligand CT. Complex 1 shows photoisomerization behavior opposite to that of azobenzene: trans‐to‐cis and cis‐to‐trans conversions proceed with 405 and 312 nm irradiation, which correspond to excitation with the intraligand CT, and π–π* bands of the azobenzene and bipyridine units, respectively. In contrast, complex 2 shows photoisomerization similar to that of azobenzene: trans‐to‐cis and cis‐to‐trans transformations occur with 365 and 405 nm irradiation, respectively. Irradiation at 578 nm, corresponding to excitation of the interligand CT transitions, results in cis‐to‐trans conversion of both 1 and 2 , which is the longest wavelength ever reported to effect the photoisomerization of the azobenzene group. The absorption and photochromism of 4 , which has azobenzene groups on both the dithiolato and bipyridine ligands, have characteristics quite similar to those of 1 and 2 , which furnishes 4 with photocontrollable tristability in a single molecule using light at 365, 405, and 578 nm. We also clarified that 1 and 2 have high photoisomerization efficiencies, and good thermal stability of the cis forms. Complexes 3 and 5 have almost the identical photoresponse to those of their positional isomers, complexes 2 and 4 . 相似文献
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Synthesis and Reactivity of a Neutral,Three‐Coordinate Platinum(II) Complex Featuring Terminal Amido Ligation 下载免费PDF全文
Colin M. Kelly Doo‐Hyun Kwon Dr. Michael J. Ferguson Dr. Steven M. Bischof Dr. Orson L. Sydora Prof. Dr. Daniel H. Ess Prof. Dr. Mark Stradiotto Prof. Dr. Laura Turculet 《Angewandte Chemie (International ed. in English)》2015,54(48):14498-14502
A crystallographically characterized three‐coordinate, formally 14 electron PtII complex 1 featuring terminal amido ligation is reported. Computational analysis revealed relatively weak π donation from the amide lone pair to platinum and supports a 14‐electron assignment for 1 . Stoichiometric reactivity studies confirmed the viability of net O? H and C? H addition across, as well as isonitrile insertion into, the terminal platinum–amido linkage of 1 . 相似文献
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Studies on [PtCl2]‐ or [AuCl]‐Catalyzed Cyclization of 1‐(Indol‐2‐yl)‐2,3‐Allenols: The Effects of Water/Steric Hindrance and 1,2‐Migration Selectivity 下载免费PDF全文
Youai Qiu Prof. Dr. Chunling Fu Prof. Dr. Xue Zhang Prof. Dr. Shengming Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10314-10322
The [PtCl2]‐ or [AuCl]‐catalyzed reaction of 1‐(indol‐2‐yl)‐2,3‐allenols occurred smoothly at room temperature to afford a series of poly‐substituted carbazoles efficiently. Compared with the [PtCl2]‐catalyzed process, the [AuCl]‐catalyzed reaction represents a significant advance in terms of the scope and the selectivity. Selective 1,2‐alkyl or aryl migration of the gold carbene intermediate was observed: compared with the methyl group, the isopropyl, cyclopropyl, cyclobutyl, and cyclohexyl groups migrate exclusively; the cyclopropyl group shifts selectively over the ethyl group; the 1,2‐migration of a non‐methyl linear alkyl is faster than methyl group; the phenyl group migrates exclusively over methyl or ethyl group. DFT calculations show that water makes the elimination of H2O facile requiring a much lower energy and validates the migratory preferences of different alkyl or phenyl groups observed. 相似文献
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Platinum trans‐Bis(borirene) Complexes Displaying Coplanarity and Communication Across a Platinum Metal Center 下载免费PDF全文
Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Rian D. Dewhurst Hauke Kelch Bret B. Macha Dr. Krzysztof Radacki Dr. Alfredo Vargas Dr. Qing Ye 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2377-2386
Ambient‐temperature photolysis of the aminoborylene complex [(OC)5Cr?B?N(SiMe3)2] in the presence of a series of trans‐bis(alkynyl)platinum(II) precursors of the type trans‐[Pt(CCAr)2(PEt3)2] (Ar=Ph, p‐C6H4OMe, and p‐C6H4CF3) successfully leads to twofold transfer of the borylene moiety [ : B?N(SiMe3)2] onto the alkyne functionalities. The alkynyl precursors and resultant bis(borirene)platinum(II) complexes formed are of the type trans‐[Pt(B{?N(SiMe3)2}C?CAr)2(PEt3)2] (Ar=Ph, p‐C6H4OMe, and p‐C6H4CF3). These species have all been successfully characterized by NMR, IR, and UV/Vis spectroscopy as well as by elemental analysis. Single‐crystal X‐ray diffraction has verified that these trans‐bis(borirene)platinum(II) complexes display coplanarity between the twin three‐membered rings across the platinum core in the solid state and stand as the first examples of coplanar conformations of twin borirene systems. These complexes were modeled using density functional theory (DFT), providing information helpful in determining the ability of the transition metal core to interact with each individual borirene ring system and allowing for the observed coplanarity of these rings in the solid state. This proposed transition metal interaction with the twin borirene systems is manifested in the electronic characterization of these borirene species, which display divergent photophysical UV/Vis spectroscopic profiles compared to a previously published mono(borirene)platinum(II) complex. 相似文献
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Dipl.‐Chem. Jürgen Bauer Prof. Dr. Holger Braunschweig Dipl.‐Chem. Peter Brenner Dipl.‐Chem. Katharina Kraft Dr. Krzysztof Radacki Dipl.‐Chem. Katrin Schwab 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(39):11985-11992
Syntheses of the first heteroleptic N‐heterocyclic carbene (NHC)–phosphane platinum(0) complexes and formation of the corresponding Lewis acid–base adducts with aluminum chloride is reported. The influence of N‐heterocyclic carbenes on tuning the Lewis basic properties of the metal complexes was judged from spectroscopic, structural, and computational data. Conclusive experimental evidence for the enhanced Lewis basicity of NHC‐containing complexes was provided by a transfer reaction. 相似文献
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Exploring Excited‐State Tunability in Luminescent Tris‐cyclometalated Platinum(IV) Complexes: Synthesis of Heteroleptic Derivatives and Computational Calculations 下载免费PDF全文
Fabio Juliá Dr. Gabriel Aullón Dr. Delia Bautista Dr. Pablo González‐Herrero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17346-17359
The synthesis, structure, electrochemistry, and photophysical properties of a series of heteroleptic tris‐ cyclometalated PtIV complexes are reported. The complexes mer‐[Pt(C^N)2(C′^N′)]OTf, with C^N=C‐deprotonated 2‐(2,4‐difluorophenyl)pyridine (dfppy) or 2‐phenylpyridine (ppy), and C′^N′=C‐deprotonated 2‐(2‐thienyl)pyridine (thpy) or 1‐phenylisoquinoline (piq), were obtained by reacting bis‐ cyclometalated precursors [Pt(C^N)2Cl2] with AgOTf (2 equiv) and an excess of the N′^C′H pro‐ligand. The complex mer‐[Pt(dfppy)2(ppy)]OTf was obtained analogously and photoisomerized to its fac counterpart. The new complexes display long‐lived luminescence at room temperature in the blue to orange color range. The emitting states involve electronic transitions almost exclusively localized on the ligand with the lowest π–π* energy gap and have very little metal character. DFT and time‐dependent DFT (TD‐DFT) calculations on mer‐[Pt(ppy)2(C′^N′)]+ (C′^N′=thpy, piq) and mer/fac‐[Pt(ppy)3]+ support this assignment and provide a basis for the understanding of the luminescence of tris‐cyclometalated PtIV complexes. Excited states of LMCT character may become thermally accessible from the emitting state in the mer isomers containing dfppy or ppy as chromophoric ligands, leading to strong nonradiative deactivation. This effect does not operate in the fac isomers or the mer complexes containing thpy or piq, for which nonradiative deactivation originates mainly from vibrational coupling to the ground state. 相似文献
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Elizabeth Suk‐Hang Lam Daniel Ping‐Kuen Tsang Dr. Wai Han Lam Dr. Anthony Yiu‐Yan Tam Dr. Mei‐Yee Chan Prof. Dr. Wing‐Tak Wong Prof. Dr. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(20):6385-6397
A series of luminescent platinum(II) complexes of tridentate 1,3‐bis(N‐alkylbenzimidazol‐2′‐yl)benzene (bzimb) ligands has been synthesized and characterized. One of these platinum(II) complexes has been structurally characterized by X‐ray crystallography. Their electrochemical, electronic absorption, and luminescence properties have been investigated. Computational studies have been performed on this class of complexes to elucidate the origin of their photophysical properties. Some of these complexes have been utilized in the fabrication of organic light‐emitting diodes (OLEDs) by using either vapor deposition or spin‐coating techniques. Chloroplatinum(II)? bzimb complexes that are functionalized at the 5‐position of the aryl ring, [Pt(R‐bzimb)Cl], not only show tunable emission color but also exhibit high current and external quantum efficiencies in OLEDs. Concentration‐dependent dual‐emissive behavior was observed in multilayer OLEDs upon the incorporation of pyrenyl ligand into the Pt(bzimb) system. Devices doped with low concentrations of the complexes gave rise to white‐light emission, thereby representing a unique class of small‐molecule, platinum(II)‐based white OLEDs. 相似文献
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Sulfur, a pollutant known to poison fuel‐cell electrodes, generally comes from S‐containing species such as hydrogen sulfide (H2S). The S‐containing species become adsorbed on a metal electrode and leave atomic S strongly bound to the metal surface. This surface sulfur is completely removed typically by oxidation with O2 into gaseous SO2. According to our DFT calculations, the oxidation of sulfur at 0.25 ML surface sulfur coverage on pure Pt(111) and Ni(111) metal surfaces is exothermic. The barriers to the formation of SO2 are 0.41 and 1.07 eV, respectively. Various metals combined to form bimetallic surfaces are reported to tune the catalytic capabilities toward some reactions. Our results show that it is more difficult to remove surface sulfur from a Ni@Pt(111) surface with reaction barrier 1.86 eV for SO2 formation than from a Pt@Ni(111) surface (0.13 eV). This result is in good agreement with the statement that bimetallic surfaces could demonstrate more or less activity than to pure metal surfaces by comparing electronic and structural effects. Furthermore, by calculating the reaction free energies we found that the sulfur oxidation reaction on the Pt@Ni(111) surface exhibits the best spontaneity of SO2 desorption at either room temperature or high temperatures. 相似文献
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Dr. Kartik Chandra Mondal Dr. Sudipta Roy Priv.‐Doz. Dr. Birger Dittrich Dr. Diego M. Andrada Prof. Dr. Gernot Frenking Prof. Dr. Herbert W. Roesky 《Angewandte Chemie (International ed. in English)》2016,55(9):3158-3161
Reduction of the neutral carbene tetrachlorosilane adduct (cAAC)SiCl4 (cAAC=cyclic alkyl(amino) carbene :C(CMe2)2(CH2)N(2,6‐iPr2C6H3) with potassium graphite produces stable (cAAC)3Si3, a carbene‐stabilized triatomic silicon(0) molecule. The Si?Si bond lengths in (cAAC)3Si3 are 2.399(8), 2.369(8) and 2.398(8) Å, which are in the range of Si?Si single bonds. Each trigonal pyramidal silicon atom of the triangular molecule (cAAC)3Si3 possesses a lone pair of electrons. Its bonding, stability, and electron density distributions were studied by quantum chemical calculations. 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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Back Cover: Exploring Excited‐State Tunability in Luminescent Tris‐cyclometalated Platinum(IV) Complexes: Synthesis of Heteroleptic Derivatives and Computational Calculations (Chem. Eur. J. 52/2014) 下载免费PDF全文
Fabio Juliá Dr. Gabriel Aullón Dr. Delia Bautista Dr. Pablo González‐Herrero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17660-17660