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1.
Ilia A. Guzei Lara C. Spencer Stephen O. Ojwach James Darkwa 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(3):m114-m116
The title compound {2‐[3,5‐bis(trifluoromethyl)‐1H‐pyrazol‐1‐ylmethyl]‐6‐(3,5‐dimethyl‐1H‐pyrazol‐1‐ylmethyl)pyridine}methylpalladium(II) tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate, [Pd(C18H18F6N5)][B(C8H3F6)4], crystallizes as discrete cations and anions. The cation possesses a pseudo‐twofold axis about which positional disorder of the tridentate ligand is exhibited. The four substituents on the two pyrazole rings exhibit CH3/CF3 disorder, while all other atoms are ordered. Thus, this disorder can be conveniently described `locally' as compositional, while `globally' for the entire tridentate ligand it is positional. The anion also exhibits typical rotational positional disorder in three of the CF3 groups. All disordered CF3 groups were modeled with idealized C3v geometry. 相似文献
2.
New isocyanide ligands with meta‐terphenyl backbones were synthesized. 2,6‐Bis[3,5‐bis(trimethylsilyl)phenyl]‐4‐methylphenyl isocyanide exhibited the highest rate acceleration in rhodium‐catalyzed hydrosilylation among other isocyanide and phosphine ligands tested in this study. 1H NMR spectroscopic studies on the coordination behavior of the new ligands to [Rh(cod)2]BF4 indicated that 2,6‐bis[3,5‐bis(trimethylsilyl)phenyl]‐4‐methylphenyl isocyanide exclusively forms the biscoordinated rhodium–isocyanide complex, whereas less sterically demanding isocyanide ligands predominantly form tetracoordinated rhodium–isocyanide complexes. FTIR and 13C NMR spectroscopic studies on the hydrosilylation reaction mixture with the rhodium–isocyanide catalyst showed that the major catalytic species responsible for the hydrosilylation activity is the Rh complex coordinated with the isocyanide ligand. DFT calculations of model compounds revealed the higher affinity of isocyanides for rhodium relative to phosphines. The combined effect of high ligand affinity for the rhodium atom and the bulkiness of the ligand, which facilitates the formation of a catalytically active, monoisocyanide–rhodium species, is proposed to account for the catalytic efficiency of the rhodium–bulky isocyanide system in hydrosilylation. 相似文献
3.
Dr. Jürgen Bauer Prof. Dr. Holger Braunschweig Dr. Rian D. Dewhurst Dr. Krzysztof Radacki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(27):8797-8805
We herein report detailed investigations into the interaction of Lewis acidic fluoroboranes, for example BF2Pf (Pf=perfluorophenyl) and BF2ArF (ArF=3,5‐bis(trifluoromethyl)phenyl), with Lewis basic platinum complexes such as [Pt(PEt3)3] and [Pt(PCy3)2] (Cy=cyclohexyl). Two presumed Lewis adducts could be identified in solution and corresponding secondary products of these Lewis adducts were characterized in the solid state. Furthermore, the concept of frustrated Lewis pairs (FLP) was applied to the activation of ethene in the system [Pt(BPf3)(CH2CH2)(dcpp)] (dcpp=1,3‐bis(dicyclohexylphosphino)propane; Pf=perfluorophenyl). Finally, DFT calculations were performed to determine the interaction between the platinum‐centered Lewis bases and the boron‐centered Lewis acids. Additionally, several possible mechanisms for the oxidative addition of the boranes BF3, BCl3, and BF2ArF to the model complex [Pt(PMe3)2] are presented. 相似文献
4.
Soonchul Kang Hironobu Hayashi Tomokazu Umeyama Dr. Yoshihiro Matano Prof. Nikolai V. Tkachenko Prof. Helge Lemmetyinen Prof. Hiroshi Imahori Prof. 《化学:亚洲杂志》2008,3(12):2065-2074
Trifluoroacetic acid‐catalyzed condensation of pyrrole with electron‐deficient and sterically hindered 3,5‐bis(trifluoromethyl)benzaldehyde results in the unexpected production of a series of meso‐3,5‐bis(trifluoromethyl)phenyl‐substituted expanded porphyrins including [22]sapphyrin 2 , N‐fused [22]pentaphyrin 3 , [26]hexaphyrin 4 , and intact [32]heptaphyrin 5 together with the conventional 5,10,15,20‐tetrakis(3,5‐bis(trifluoromethyl)phenyl)porphyrin 1 . These expanded porphyrins are characterized by mass spectrometry, 1H NMR spectroscopy, UV/Vis/NIR absorption spectroscopy, and fluorescence spectroscopy. The optical and electrochemical measurements reveal a decrease in the HOMO–LUMO gap with increasing size of the conjugated macrocycles, and in accordance with the trend, the deactivation of the excited singlet state to the ground state is enhanced. 相似文献
5.
Gary L. Guillet Skyler L. Pitts Kirkland W. Sheriff Donna N. Rucker Aaryn L. Rogers 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(10):1381-1388
A novel family of four 1‐bromo‐2,6‐bis{[(λ5‐phosphanylidene)imino]methyl}benzene ligands has been synthesized and characterized. The phosphiniminomethyl substituents are decorated with either three phenyl groups, two phenyl and one cyclohexyl group, one phenyl and two cyclohexyl groups, or three cyclohexyl groups. Each ligand was metallated using zero‐valent nickel through an oxidative addition to form a family of organonickel(II) complexes, namely (2,6‐bis{[(triphenyl‐λ5‐phosphanylidene)imino]methyl}phenyl‐κ3N,C1,N′)bromidonickel(II) dichloromethane hemisolvate, [NiBr(C44H37N2P2)]·0.5CH2Cl2, (2,6‐bis{[(cyclohexyldiphenyl‐λ5‐phosphanylidene)imino]methyl}phenyl‐κ3N,C1,N′)bromidonickel(II) diethyl ether hemisolvate, [NiBr(C44H49N2P2)]·0.5C4H10O, (2,6‐bis{[(dicyclohexylphenyl‐λ5‐phosphanylidene)imino]methyl}phenyl‐κ3N,C1,N′)bromidonickel(II), [NiBr(C44H61N2P2)], and (2,6‐bis{[(tricyclohexyl‐λ5‐phosphanylidene)imino]methyl}phenyl‐κ3N,C1,N′)bromidonickel(II), [NiBr(C44H73N2P2)]. This family of complexes represents a useful opportunity to investigate the impact of incrementally changing the steric characteristics of a complex on its structure and reactivity. 相似文献
6.
Pravinchandra J. Vankawala Naveenkumar Kolla Chandrashekar R. Elati M. Sreenivasulu K. Arun Kumar Yerrimilli Anjaneyulu 《合成通讯》2013,43(19):3439-3446
Enzyme‐catalyzed efficient synthesis of (1R)‐[3,5‐bis (trifluoromethyl) phenyl] ethanol (R)‐(3), a key intermediate for aprepitant, via enantioselective transesterification of racemic 1‐[3,5‐bis (trifluoromethyl) phenyl] ethanol (RS)‐3 using vinyl acetate as the acyl donor in the presence of Candida antarctica lipase‐B (CAL‐B) in an overall yield of 84% with >99% ee is described. 相似文献
7.
Maddalena Corsini Piero Zanello Renzo Cini Gabriella Tamasi 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(6):m219-m223
The title compound, [Cu(C10H9N2O)2] or [CuII(CYMB)2], (I), was obtained in an attempt to reduce trans‐bis(2‐{[3,5‐bis(trifluoromethyl)phenyl]iminomethyl}phenolato)copper(II), [Cu(TIMB)2], (II), with bis(pentamethylcyclopentadienyl)cobalt(II) [decamethylcobaltocene, Cp*2Co, (III)]. The molecular structure of (I) has the CuII centre located on an inversion centre of the C2/c space group. A density functional theory (DFT) analysis at the B3LYP/Lanl2dz(CuF);6‐31G**(CHNO) level performed in order to optimize the structures of the free ligands CYMB− and TIMB−, and the metal complexes [CuI/II(CYMB)2]−/0 and [CuI/II(TIMB)2]−/0, reproduced well the X‐ray diffraction structure and allowed us to infer the insertion of the cyanomethide anion on the 3,5‐bis(trifluoromethyl)phenyl system from an evaluation of the Mulliken atomic charges and the electronic energies. 相似文献
8.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(10):1171-1179
3,5‐Bis(arylidene)‐4‐piperidone (BAP) derivatives display good antitumour and anti‐inflammatory activities because of their double α,β‐unsaturated ketone structural characteristics. If N‐benzenesulfonyl substituents are introduced into BAPs, the configuration of the BAPs would change significantly and their anti‐inflammatory activities should improve. Four N‐benzenesulfonyl BAPs, namely (3E,5E)‐1‐(4‐methylbenzenesulfonyl)‐3,5‐bis[4‐(trifluoromethyl)benzylidene]piperidin‐4‐one dichloromethane monosolvate, C28H21F6NO3S·CH2Cl2, ( 4 ), (3E,5E)‐1‐(4‐fluorobenzenesulfonyl)‐3,5‐bis[4‐(trifluoromethyl)benzylidene]piperidin‐4‐one, C27H18F7NO3S, ( 5 ), (3E,5E)‐1‐(4‐nitrobenzenesulfonyl)‐3,5‐bis[4‐(trifluoromethyl)benzylidene]piperidin‐4‐one, C27H18F6N2O5S, ( 6 ), and (3E,5E)‐1‐(4‐cyanobenzenesulfonyl)‐3,5‐bis[4‐(trifluoromethyl)benzylidene]piperidin‐4‐one dichloromethane monosolvate, C28H18F6N2O3S·CH2Cl2, ( 7 ), were prepared by Claisen–Schmidt condensation and N‐sulfonylation. They were characterized by NMR, FT–IR and HRMS (high resolution mass spectrometry). Single‐crystal structure analysis reveals that the two 4‐(trifluoromethyl)phenyl rings on both sides of the piperidone ring in ( 4 )–( 7 ) adopt an E stereochemistry of the olefinic double bonds. Molecules of both ( 4 ) and ( 6 ) are connected by hydrogen bonds into one‐dimensional chains. In ( 5 ) and ( 7 ), pairs of adjacent molecules embrace through intermolecular hydrogen bonds to form a bimolecular combination, which are further extended into a two‐dimensional sheet. The anti‐inflammatory activity data reveal that ( 4 )–( 7 ) significantly inhibit LPS‐induced interleukin (IL‐6) and tumour necrosis factor (TNF‐α) secretion. Most importantly, ( 6 ) and ( 7 ), with strong electron‐withdrawing substituents, display more potential inhibitory effects than ( 4 ) and ( 5 ). 相似文献
9.
Pradip K. Bhowmik Haesook Han Ivan K. Ndedeltchev James J. Cebe Shin‐Woong Kang Satyendra Kumar 《Liquid crystals》2013,40(8):891-906
Several viologen bis{tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate} salts were prepared by metathesis reaction of the corresponding viologen dibromides (diiodide) with sodium bis{tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate} salt in a polar organic solvent. They were characterized for their physical and thermal properties by experimental techniques including variable temperature X‐ray diffraction. All exhibited low T g and T m, and their T g/T m (K) ratios were in the range 0.66–0.79. Several exhibited polymorphism and formed isotropic ionic melts at <150°C. They were soluble in many common organic solvents such as ethers, alcohols, acetonitrile and methylene chloride. They exhibited photoluminescence in both 1,2‐dimethoxyethane and methanol, as well as in the solid state. In the solid state, the emission spectra exhibited hypsochromic shift when compared with those in solutions of 1,2‐dimethoxyethane and methanol. 相似文献
10.
J. G. Liu Z. X. Li J. T. Wu H. W. Zhou F. S. Wang S. Y. Yang 《Journal of polymer science. Part A, Polymer chemistry》2002,40(10):1583-1593
Fluorinated copolyimides derived from 4,4′‐oxydiphthalic anhydride (ODPA) with 4,4′‐oxydianline (ODA) and trifluoromethyl‐containing aromatic diamines have been synthesized and characterized. The trifluoromethyl‐containing diamines include 2,4‐diamino‐3′‐trifluoromethylazobenzene, 2,4‐diamino‐1‐[(4′‐trifluoromethylphenoxy) phenyl] aniline, 3,5‐diamino‐1‐[(4′‐trifluoromethylphenoxy) phenyl] benzamide, 3,5‐diamino‐1‐[(3′‐trifluoromethyl) phenyl] benzamide, 1,4‐bis(4′‐aminophenoxy)‐2‐(3′‐trifluoromethylphenyl) benzene, 3,5‐diaminobenzenetrifluoride, 4,4′‐diamino‐4″‐(p‐trifluoromethyl phenoxy) triphenylamine, and 4‐[(4′‐trifluoromethylphenoxy) phenyl]‐2,6‐bis(4″‐aminophenyl)pyridine. Strong and flexible copolyimide films, produced by casting the polyamic acid solution followed by thermal imidization, exhibited great thermal stability and high mechanical properties. The polyimides had an ultraviolet–visible absorption cutoff at 330–340 nm and pretilt angles as high as 20° for nematic liquid crystals, making them great potential candidates for advanced liquid‐crystal display applications. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1583–1593, 2002 相似文献
11.
An Ethylene‐Bridged Phosphane/Borane Frustrated Lewis Pair Featuring the ‐B(Fxyl)2 Lewis Acid Component
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Dr. Long Wang Kamil Samigullin Prof. Dr. Matthias Wagner Dr. Alison C. McQuilken Prof. Dr. Timothy H. Warren Dr. Constantin G. Daniliuc Dr. Gerald Kehr Prof. Dr. Gerhard Erker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(31):11015-11021
Hydroboration of dimesitylvinylphosphane with bis[3,5‐bis(trifluoromethyl)phenyl]borane [HB(Fxyl)2] gave the intramolecular ethylene‐bridged P/B frustrated Lewis pair (FLP) Mes2PCH2CH2B(Fxyl)2. The new compound underwent a variety of typical FLP reactions such as P/B‐addition to the carbonyl group of p‐chloro‐benzaldehyde. Cooperative N,N‐addition to nitric oxide gave the respective persistent P/B FLPNO. radical, which readily reacted with 1,4‐cyclohexadiene by H‐atom abstraction to yield the corresponding P/B FLPNOH product. The B(Fxyl)2‐containing FLP reacted as a template for the HB(C6F5)2 reduction of carbon monoxide to the formyl stage to give the respective FLP(η2‐formylborane) product. Most products were characterized by single‐crystal X‐ray crystal structure analysis. 相似文献
12.
Boron Lewis Acid‐Catalyzed Hydroboration of Alkenes with Pinacolborane: BArF3 Does What B(C6F5)3 Cannot Do!
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Dr. Qin Yin Dr. Hendrik F. T. Klare Prof. Dr. Martin Oestreich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(39):13840-13844
The transition‐metal‐free hydroboration of various alkenes with pinacolborane (HBpin) initiated by tris[3,5‐bis(trifluoromethyl)phenyl]borane (BArF3) is reported. The choice of the boron Lewis acid is crucial as the more prominent boron Lewis acid tris(pentafluorophenyl)borane (B(C6F5)3) is reluctant to react. Unlike B(C6F5)3, BArF3 is found to engage in substituent redistribution with HBpin, resulting in the formation of ArFBpin and the electron‐deficient diboranes [H2BArF]2 and [(ArF)(H)B(μ‐H)2BArF2]. These in situ‐generated hydroboranes undergo regioselective hydroboration of styrene derivatives as well as aliphatic alkenes with cis diastereoselectivity. Another ligand metathesis of these adducts with HBpin subsequently affords the corresponding HBpin‐derived anti‐Markovnikov adducts. The reactive hydroboranes are regenerated in this step, thereby closing the catalytic cycle. 相似文献
13.
Highly Stereoselective β‐Mannopyranosylation via the 1‐α‐Glycosyloxy‐isochromenylium‐4‐gold(I) Intermediates
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While the gold(I)‐catalyzed glycosylation reaction with 4,6‐O‐benzylidene tethered mannosyl ortho‐alkynylbenzoates as donors falls squarely into the category of the Crich‐type β‐selective mannosylation when Ph3PAuOTf is used as the catalyst, in that the mannosyl α‐triflates are invoked, replacement of the ?OTf in the gold(I) complex with less nucleophilic counter anions (i.e., ?NTf2, ?SbF6, ?BF4, and ?BAr4F) leads to complete loss of β‐selectivity with the mannosyl ortho‐alkynylbenzoate β‐donors. Nevertheless, with the α‐donors, the mannosylation reactions under the catalysis of Ph3PAuBAr4F (BAr4F=tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate) are especially highly β‐selective and accommodate a broad scope of substrates; these include glycosylation with mannosyl donors installed with a bulky TBS group at O3, donors bearing 4,6‐di‐O‐benzoyl groups, and acceptors known as sterically unmatched or hindered. For the ortho‐alkynylbenzoate β‐donors, an anomerization and glycosylation sequence can also ensure the highly β‐selective mannosylation. The 1‐α‐mannosyloxy‐isochromenylium‐4‐gold(I) complex ( Cα ), readily generated upon activation of the α‐mannosyl ortho‐alkynylbenzoate ( 1 α ) with Ph3PAuBAr4F at ?35 °C, was well characterized by NMR spectroscopy; the occurrence of this species accounts for the high β‐selectivity in the present mannosylation. 相似文献
14.
Saskia Mller Hans-Joachim Drexler Detlef Heller 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(10):1434-1438
The complexes {bis[(2‐diphenylphosphanyl)phenyl] ether‐κ2P,P′}(η4‐norbornadiene)rhodium(I) tetrafluoridoborate, [Rh(C7H8)(C36H28OP2)]BF4, and {bis[(2‐diphenylphosphanyl)phenyl] ether‐κ2P,P′}[η4‐(Z,Z)‐cycloocta‐1,5‐diene]rhodium(I) tetrafluoridoborate dichloromethane monosolvate, [Rh(C8H12)(C36H28OP2)]BF4·CH2Cl2, are applied as precatalysts in redox‐neutral atomic‐economic propargylic CH activation [Lumbroso et al. (2013). Angew. Chem. Int. Ed. 52 , 1890–1932]. In addition, the catalytically inactive pentacoordinated 18‐electron complex {bis[(2‐diphenylphosphanyl)phenyl] ether‐κ2P,P′}chlorido(η4‐norbornadiene)rhodium(I), [RhCl(C7H8)(C36H28OP2)], was synthesized, which can form in the presence of chloride in the reaction system. 相似文献
15.
Synthesis and Characterization of m‐Terphenyl (1,3‐Diphenylbenzene) Compounds Containing Trifluoromethyl Groups
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Alma T. Corona‐Armenta Mario Ordoñez Jorge A. López Jorge Cervantes Oracio Serrano 《Helvetica chimica acta》2015,98(3):359-367
The bis(silyl)triazene compound 2,6‐(Me3Si)2‐4‐Me‐1‐(N?N? NC4H8)C6H2 ( 4 ) was synthesized by double lithiation/silylation of 2,6‐Br2‐4‐Me‐1‐(N?N? NC4H8)C6H2 ( 1 ). Furthermore, 2,6‐bis[3,5‐(CF3)2‐C6H3]‐4‐Me‐C6H2‐1‐(N?N? NC4H8)C6H2 derivative 6 can be easily synthesized by a C,C‐bond formation reaction of 1 with the corresponding aryl‐Grignard reagent, i.e., 3,5‐bis[(trifluoromethyl)phenyl]magnesium bromide. Reactions of compound 4 with KI and 6 with I2 afforded in good yields novel phenyl derivatives, 2,6‐(Me3Si)2‐4‐MeC6H2? I and 2,6‐bis[3,5‐(CF3)2? C6H3]‐4‐MeC6H2? I ( 5 and 7 , resp.). On the other hand, the analogous m‐terphenyl 1,3‐diphenylbenzene compound 2,6‐bis[3,5‐(CF3)2? C6H3]C6H3? I ( 8 ) could be obtained in moderate yield from the reaction of (2,6‐dichlorophenyl)lithium and 2 equiv. of aryl‐Grignard reagent, followed by the reaction with I2. Different attempts to introduce the tBu (Me3C) or neophyl (PhC(Me)2CH2) substituents in the central ring were unsuccessful. All the compounds were fully characterized by elemental analysis, melting point, IR and NMR spectroscopy. The structure of compound 6 was corroborated by single‐crystal X‐ray diffraction measurements. 相似文献
16.
Berthold Hoge Dr. Boris Kurscheid Sebastian Peuker Wieland Tyrra Hendrik T. M. Fischer 《无机化学与普通化学杂志》2007,633(10):1679-1685
The reaction of the sterically shielded phosphane derivative, dichlorodiethylaminophosphane, Cl2PNEt2, with an excess of a mixture of 2,6‐bis(trifluoromethyl) and 2,4‐bis(trifluoromethyl)phenyl lithium gives bis[2,4‐bis(trifluoromethyl)phenyl]diethylaminophosphane, [2,4‐(CF3)2C6H3]2PNEt2, in 72 % yield as a colourless solid, while 2,6‐bis(trifluoromethyl)phenyl lithium remains unchanged in solution. The amino derivative crystallizes in the monoclinic space group P21/c (a 869.2(1), b 1857.4(1), c 1357.6(1) pm, β 100.57(4)°, Z = 4). Treatment of [2,4‐(CF3)2C6H3]2PNEt2 in CHCl3 solution with conc. HCl allows the synthesis of [2,4‐(CF3)2C6H3)]2PCl. [2,4‐(CF3)2C6H3]2PCl reacts with H2O in THF solution with quantitative formation of the corresponding secondary phosphane oxide. To obtain bis[2,4‐bis(trifluoromethyl)phenyl]phosphinic acid, [2,4‐(CF3)2C6H3]2P(O)OH, quantitatively, a CHCl3 solution of [2,4‐(CF3)2C6H3]2P(O)H, has to be stirred in an NO2 atmosphere. The phosphinic acid crystallizes is the triclinic space group (a 754.2(1), b 927.6(2), c 1305.5(2) pm, α 85.11(2)°, β 75.45(1)°, γ 79.99(2)°, Z = 2). From the reaction of the phosphinic acid with either elemental sodium or with cyanide salts, the corresponding phosphinate salts are obtained in an almost quantitatively yield. 相似文献
17.
Antonio Currao Nantko Feiken Alceo Macchioni Reinhard Nesper Paul S. Pregosin Gerald Trabesinger 《Helvetica chimica acta》1996,79(6):1587-1591
The ligand (6,6′-dimethoxybiphenyl-2,2′-diyl)bis[3,5-di(tert-butyl)phenylphosphine] ( 1 ) forms an unexpectedly stable hydrido-bis-solvento complex of composition [RuH(isopropanol)2( 1 )]BF4, ( 2 ) under the conditions used in the enantioselective hydrogenation of pyrones. The structure of 2 , determined by X-ray diffraction, represents the first well-characterized chiral five-coordinate bis-phosphine ruthenium-hydride complex stable as a solvento complex, and provides a structural link in the enantioselective pyrone hydrogenation cycle catalyzed by [Ru(OAc)2( 1 )]. Using the arene complex [RuH(p-cymene)( 1 )]BF4 ( 3 ), the chiral pocket of coordinated 1 is shown to be relatively rigid, via NMR spectroscopy. This is reflected in restricted rotation about one of the four P–[3,5-di(tert-butyl)phenyl] P? Cipso bonds at room temperature. 相似文献
18.
Subporpholactone,Subporpholactam, Imidazolosubporphyrin,and Iridium Complexes of Imidazolosubporphyrin: Formation of Iridium Carbene Complexes
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Kota Yoshida Prof. Dr. Atsuhiro Osuka 《Angewandte Chemie (International ed. in English)》2018,57(1):338-342
Pyrrole‐modified subporphyrins bearing a non‐pyrrolic cyclic unit, subporpholactone, subporpholactam, and imidazolosubporphyrin were newly synthesized. They show subporphyrin‐like absorption and fluorescence spectra that are red‐shifted in the order of subporpholactam<subporpholactone<imidazolosubporphyrin. Metalation of the imidazolosubporphyrin with (pentamethylcyclopentadienyl)iridium(III) dichloride dimer gave a complex, in which the iridium(III) atom was attached at the peripheral nitrogen atom of the imidazole moiety and the ortho‐position of the meso‐phenyl group. Reaction of this complex with diphenylacetylene gave different products depending on the used additive; a phenyl‐rearranged product in the presence of NaBArF4 (ArF=3,5‐bis(trifluoromethyl)phenyl) and two isomeric carbene complexes in the presence of KPF6. 相似文献
19.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(1):344-348
Pyrrole‐modified subporphyrins bearing a non‐pyrrolic cyclic unit, subporpholactone, subporpholactam, and imidazolosubporphyrin were newly synthesized. They show subporphyrin‐like absorption and fluorescence spectra that are red‐shifted in the order of subporpholactam<subporpholactone<imidazolosubporphyrin. Metalation of the imidazolosubporphyrin with (pentamethylcyclopentadienyl)iridium(III) dichloride dimer gave a complex, in which the iridium(III) atom was attached at the peripheral nitrogen atom of the imidazole moiety and the ortho‐position of the meso‐phenyl group. Reaction of this complex with diphenylacetylene gave different products depending on the used additive; a phenyl‐rearranged product in the presence of NaBArF4 (ArF=3,5‐bis(trifluoromethyl)phenyl) and two isomeric carbene complexes in the presence of KPF6. 相似文献
20.
Dr. Eugene L. Kolychev Dr. Thomas Bannenberg Dr. Matthias Freytag Dr. Constantin G. Daniliuc Prof. Dr. Peter G. Jones Prof. Dr. Matthias Tamm 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(52):16938-16946
Tris[3,5‐bis(trifluoromethyl)phenyl]borane reacts with the sterically demanding Arduengo carbenes 1,3‐di‐tert‐butylimidazolin‐2‐ylidene and 1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene to form isolable normal adducts. In the case of 1,3‐di‐tert‐butylimidazolin‐2‐ylidene, the adduct exhibits dynamic behaviour in solution and frustrated‐Lewis‐pair (FLP) reactivity. Fast cleavage of dihydrogen and THF, the C? H activation of phenylacetylene, and carbon dioxide fixation were achieved by using solutions of this adduct in benzene. This adduct is stable at room temperature in the absence of suitable substrates; however, thermal rearrangement into an abnormal carbene–borane adduct can be observed. In contrast, the 1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene adduct exhibits no evidence of FLP reactivity or of dissociation in solution. DFT calculations confirmed the experimental behaviour and stability of these carbene–borane adducts. 相似文献