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Tae‐Jin Kim Sung‐Kwan Kim Beom‐Jun Kim Ho‐Jin Son Jong Sok Hahn Minserk Cheong Prof. Mariusz Mitoraj Dr. Monika Srebro Łukasz Piękoś Artur Michalak Prof. Sang Ook Kang Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(19):5630-5644
A series of mono‐, bis‐, and tris(phenoxy)–titanium(IV) chlorides of the type [Cp*Ti(2‐R? PhO)nCl3?n] (n=1–3; Cp*=pentamethylcyclopentadienyl) was prepared, in which R=Me, iPr, tBu, and Ph. The formation of each mono‐, bis‐, and tris(2‐alkyl‐/arylphenoxy) series was authenticated by structural studies on representative examples of the phenyl series including [Cp*Ti(2‐Ph? PhO)Cl2] ( 1 PhCl2 ), [Cp*Ti(2‐Ph? PhO)2Cl] ( 2 PhCl ), and [Cp*Ti(2‐Ph? PhO)3] ( 3 Ph ). The metal‐coordination geometry of each compound is best described as pseudotetrahedral with the Cp* ring and the 2‐Ph? PhO and chloride ligands occupying three leg positions in a piano‐stool geometry. The mean Ti? O distances, observed with an increasing number of 2‐Ph? PhO groups, are 1.784(3), 1.802(4), and 1.799(3) Å for 1 PhCl2 , 2 PhCl , and 3 Ph , respectively. All four alkyl/aryl series with Me, iPr, tBu, and Ph substituents were tested for ethylene homopolymerization after activation with Ph3C+[B(C6F5)4]? and modified methyaluminoxane (7% aluminum in isopar E; mMAO‐7) at 140 °C. The phenyl series showed much higher catalytic activity, which ranged from 43.2 and 65.4 kg (mmol of Ti?h)?1, than the Me, iPr, and tBu series (19.2 and 36.6 kg (mmol of Ti?h)?1). Among the phenyl series, the bis(phenoxide) complex of 2 PhCl showed the highest activity of 65.4 kg (mmol of Ti?h)?1. Therefore, the catalyst precursors of the phenyl series were examined by treating them with a variety of alkylating reagents, such as trimethylaluminum (TMA), triisobutylaluminum (TIBA), and methylaluminoxane (MAO). In all cases, 2 PhCl produced the most catalytically active alkylated species, [Cp*Ti(2‐Ph? PhO)MeCl]. This enhancement was further supported by DFT calculations based on the simplified model with TMA. 相似文献
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Prof. Jochen Autschbach Kiplangat Sutter Dr. Lionel A. Truflandier Dr. Erica Brendler Dr. Jörg Wagler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(40):12803-12813
New members of a novel class of metallasilatrane complexes [X‐Si‐(μ‐mt)4‐M‐Y], with M=Ni, Pd, Pt, X=F, Cl, Y=Cl, Br, I, and mt=2‐mercapto‐1‐methylimidazolide, have been synthesized and characterized structurally by X‐ray diffraction and by 29Si solid‐state NMR. Spin‐orbit (SO) effects on the 29Si chemical shifts induced by the metal, by the sulfur atoms in the ligand, and by heavy halide ligands Y=Cl, Br, I were investigated with the help of relativistic density functional calculations. Operators used in the calculations were constructed such that SO coupling can selectively be switched off for certain atoms. The unexpectedly large SO effects on the 29Si shielding in the Ni complex with X=Y=Cl reported recently originate directly from the Ni atom, not from other moderately heavy atoms in the complex. With respect to Pd, SO effects are amplified for Ni owing to its smaller ligand‐field splitting, despite the smaller nuclear charge. In the X=Cl, Y=Cl, Br, I series of complexes the Y ligand strongly modulates the 29Si shift by amplifying or suppressing the metal SO effects. The pronounced delocalization of the partially covalent M←Y bond plays an important role in modulating the 29Si shielding. We also demonstrate an influence from the X ligand on the 29Si SO shielding contributions originating at Y. The NMR spectra for [X‐Si‐(μ‐mt)4‐M‐Y] must be interpreted mainly based on electronic and relativistic effects, rather than structural differences between the complexes. The results highlight the sometimes unintuitive role of SO coupling in NMR spectra of complexes containing heavy atoms. 相似文献
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Unprecedented Spectroscopic and Computational Evidence for Allenyl and Propargyl Titanocene(IV) Complexes: Electrophilic Quenching of Their Metallotropic Equilibrium
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Ana Belén Ruiz‐Muelle Dr. Pascual Oña‐Burgos Dr. Manuel A. Ortuño Prof. Dr. J. Enrique Oltra Prof. Dr. Ignacio Rodríguez‐García Prof. Dr. Ignacio Fernández 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(7):2427-2439
The synthesis and structural characterization of allenyl titanocene(IV) [TiClCp2(CH=C=CH2)] 3 and propargyl titanocene(IV) [TiClCp2(CH2?C≡C?(CH2)4CH3)] 9 have been described for the first time. Advanced NMR methods including diffusion NMR methods (diffusion pulsed field gradient stimulated spin echo (PFG‐STE) and DOSY) have been applied and established that these organometallics are monomers in THF solution with hydrodynamic radii (from the Stokes–Einstein equation) of 3.5 and 4.1 Å for 3 and 9 , respectively. Full 1H, 13C, Δ1H, and Δ13C NMR data are given, and through the analysis of the Ramsey equation, the first electronic insights into these derivatives are provided. In solution, they are involved in their respective metallotropic allenyl–propargyl equilibria that, after quenching experiments with aromatic and aliphatic aldehydes, ketones, and protonating agents, always give the propargyl products P (when carbonyls are employed), or allenyl products A (when a proton source is added) as the major isomers. In all the cases assayed, the ratio of products suggests that the metallotropic equilibrium should be faster than the reactions of 3 and 9 with electrophiles. Indeed, DFT calculations predict lower Gibbs energy barriers for the metallotropic equilibrium, thus confirming dynamic kinetic resolution. 相似文献
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Arne Wagner Dr. Elisabeth Kaifer Prof. Dr. Hans‐Jörg Himmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(23):7395-7409
The coordination chemistry of the doubly base‐stabilised diborane(4), [HB(hpp)]2 (hpp=1,3,4,6,7,8‐hexahydro‐2H‐pyrimido‐[1,2‐a]pyrimidinate), was extended by the synthesis of new late transition‐metal complexes containing CuI and RhI fragments. A detailed experimental study was conducted and quantum‐chemical calculations on the metal–ligand bonding interactions for [HB(hpp)]2 complexes of Group 6, 9, 11 and 12 metals revealed the dominant B? H? M interactions in the case of early transition‐metal fragments, whereas the B? B? M bonding prevails in the case of the late d‐block compounds. These findings support the experimental results as reflected by the IR and NMR spectroscopic parameters of the investigated compounds. DFT calculations on [MeB(hpp)]2 and model reactions between [B2H4 ? 2NMe3] and [Rh(μ‐Cl)(C2H4)2] showed that the bicyclic guanidinate allows in principle for an oxidative addition of the B? B bond. However, the formation of σ‐complexes is thermodynamically favoured. The results point to the selective B? H or B? B bond‐activation of diborane compounds by complexation, depending on the chosen transition‐metal fragment. 相似文献
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Metal olefin complexes that are ubiquitous intermediates in catalysis are investigated by a detailed analysis of their 13C‐NMR chemical shift tensors. This analysis allows evidencing specific electronic features, namely the olefin‐to‐metal σ‐donation and the metal‐to‐olefin π‐backdonation as proposed in the Dewar?Chatt?Duncanson model. Apart from these interactions, the chemical shift tensor analysis reveals an additional ligand‐to‐metal π‐donation of the olefin σ(C=C) orbital in systems with suitably oriented vacant d‐orbitals. This interaction which is not accounted for in the Dewar?Chatt?Duncanson model explains the reactivity of this type of metal olefin complexes towards oxidative cyclization (olefin insertion) and protonolysis. 相似文献
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Crystallographic and Dynamic Aspects of Solid‐State NMR Calibration Compounds: Towards ab Initio NMR Crystallography
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Xiaozhou Li Lukas Tapmeyer Dr. Michael Bolte Dr. Jacco van de Streek 《Chemphyschem》2016,17(16):2496-2502
The excellent results of dispersion‐corrected density functional theory (DFT‐D) calculations for static systems have been well established over the past decade. The introduction of dynamics into DFT‐D calculations is a target, especially for the field of molecular NMR crystallography. Four 13C ss‐NMR calibration compounds are investigated by single‐crystal X‐ray diffraction, molecular dynamics and DFT‐D calculations. The crystal structure of 3‐methylglutaric acid is reported. The rotator phases of adamantane and hexamethylbenzene at room temperature are successfully reproduced in the molecular dynamics simulations. The calculated 13C chemical shifts of these compounds are in excellent agreement with experiment, with a root‐mean‐square deviation of 2.0 ppm. It is confirmed that a combination of classical molecular dynamics and DFT‐D chemical shift calculation improves the accuracy of calculated chemical shifts. 相似文献
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Univalent Gallium Complexes of Simple and ansa‐Arene Ligands: Effects on the Polymerization of Isobutylene
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Martin R. Lichtenthaler Steffen Maurer Robert J. Mangan Florian Stahl Florian Mönkemeyer Julian Hamann Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):157-165
Using [Ga(C6H5F)2]+[Al(ORF)4]?( 1 ) (RF=C(CF3)3) as starting material, we isolated bis‐ and tris‐η6‐coordinated gallium(I) arene complex salts of p‐xylene (1,4‐Me2C6H4), hexamethylbenzene (C6Me6), diphenylethane (PhC2H4Ph), and m‐terphenyl (1,3‐Ph2C6H4): [Ga(1,4‐Me2C6H4)2.5]+ ( 2+ ), [Ga(C6Me6)2]+ ( 3+ ), [Ga(PhC2H4Ph)]+ ( 4+ ) and [(C6H5F)Ga(μ‐1,3‐Ph2C6H4)2Ga(C6H5F)]2+ ( 52+ ). 4+ is the first structurally characterized ansa‐like bent sandwich chelate of univalent gallium and 52+ the first binuclear gallium(I) complex without a Ga?Ga bond. Beyond confirming the structural findings by multinuclear NMR spectroscopic investigations and density functional calculations (RI‐BP86/SV(P) level), [Ga(PhC2H4Ph)]+[Al(ORF)4]?( 4 ) and [(C6H5F)Ga(μ‐1,3‐Ph2C6H4)2Ga(C6H5F)]2+{[Al(ORF)4] ?}2 ( 5 ), featuring ansa‐arene ligands, were tested as catalysts for the synthesis of highly reactive polyisobutylene (HR‐PIB). In comparison to the recently published 1 and the [Ga(1,3,5‐Me3C6H3)2]+[Al(ORF)4]? salt ( 6 ) (1,3,5‐Me3C6H3=mesitylene), 4 and 5 gave slightly reduced reactivities. This allowed for favorably increased polymerization temperatures of up to +15 °C, while yielding HR‐PIB with high contents of terminal olefinic double bonds (α‐contents=84–93 %), low molecular weights (Mn=1000–3000 g mol?1) and good monomer conversions (up to 83 % in two hours). While the chelate complexes delivered more favorable results than 1 and 6 , the reaction kinetics resembled and thus concurred with the recently proposed coordinative polymerization mechanism. 相似文献
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Dr. Evanildo G. Lacerda Jr. Dr. Fadhil S. Kamounah Prof. Dr. Kaline Coutinho Prof. Dr. Stephan P. A. Sauer Prof. Dr. Poul Erik Hansen Prof. Dr. Ole Hammerich 《Chemphyschem》2019,20(1):78-91
Prediction of chemical shifts in organic cations is known to be a challenge. In this article we meet this challenge for α-protonated alkylpyrroles, a class of compounds not yet studied in this context, and present a combined experimental and theoretical study of the 13C and 1H chemical shifts in three selected pyrroles. We have investigated the importance of the solvation model, basis set, and quantum chemical method with the goal of developing a simple computational protocol, which allows prediction of 13C and 1H chemical shifts with sufficient accuracy for identifying such compounds in mixtures. We find that density functional theory with the B3LYP functional is not sufficient for reproducing all 13C chemical shifts, whereas already the simplest correlated wave function model, Møller–Plesset perturbation theory (MP2), leads to almost perfect agreement with the experimental data. Treatment of solvent effects generally improves the agreement with experiment to some extent and can in most cases be accomplished by a simple polarizable continuum model. The only exception is the NH proton, which requires inclusion of explicit solvent molecules in the calculation. 相似文献
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Experimental and Theoretical Studies on Arene‐Bridged Metal–Metal‐Bonded Dimolybdenum Complexes
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Dr. Mario Carrasco Natalia Curado Dr. Eleuterio Álvarez Dr. Celia Maya Dr. Riccardo Peloso Prof. Dr. Manuel L. Poveda Dr. Amor Rodríguez Prof. Dr. Eliseo Ruiz Prof. Dr. Santiago Álvarez Prof. Dr. Ernesto Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):6092-6102
The bis(hydride) dimolybdenum complex, [Mo2(H)2{HC(N‐2,6‐iPr2C6H3)2}2(thf)2], 2 , which possesses a quadruply bonded Mo2II core, undergoes light‐induced (365 nm) reductive elimination of H2 and arene coordination in benzene and toluene solutions, with formation of the MoI2 complexes [Mo2{HC(N‐2,6‐iPr2C6H3)2}2(arene)], 3?C6H6 and 3?C6H5Me , respectively. The analogous C6H5OMe, p‐C6H4Me2, C6H5F, and p‐C6H4F2 derivatives have also been prepared by thermal or photochemical methods, which nevertheless employ different Mo2 complex precursors. X‐ray crystallography and solution NMR studies demonstrate that the molecule of the arene bridges the molybdenum atoms of the MoI2 core, coordinating to each in an η2 fashion. In solution, the arene rotates fast on the NMR timescale around the Mo2‐arene axis. For the substituted aromatic hydrocarbons, the NMR data are consistent with the existence of a major rotamer in which the metal atoms are coordinated to the more electron‐rich C?C bonds. 相似文献
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The Relationship between NMR Chemical Shifts of Thermally Polarized and Hyperpolarized 89Y Complexes and Their Solution Structures
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Dr. Yixun Xing Dr. Ashish K. Jindal Dr. Martín Regueiro‐Figueroa Dr. Mariane Le Fur Nelly Kervarec Piyu Zhao Dr. Zoltan Kovacs Dr. Laura Valencia Dr. Paulo Pérez‐Lourido Prof. Raphaël Tripier Dr. David Esteban‐Gómez Dr. Carlos Platas‐Iglesias Prof. A. Dean Sherry 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16657-16667
Recently developed dynamic nuclear polarization (DNP) technology offers the potential of increasing the NMR sensitivity of even rare nuclei for biological imaging applications. Hyperpolarized 89Y is an ideal candidate because of its narrow NMR linewidth, favorable spin quantum number (I= ), and long longitudinal relaxation times (T1). Strong NMR signals were detected in hyperpolarized 89Y samples of a variety of yttrium complexes. A dataset of 89Y NMR data composed of 23 complexes with polyaminocarboxylate ligands was obtained using hyperpolarized 89Y measurements or 1H,89Y‐HMQC spectroscopy. These data were used to derive an empirical equation that describes the correlation between the 89Y chemical shift and the chemical structure of the complexes. This empirical correlation serves as a guide for the design of 89Y sensors. Relativistic (DKH2) DFT calculations were found to predict the experimental 89Y chemical shifts to a rather good accuracy. 相似文献
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Inside Back Cover: Univalent Gallium Complexes of Simple and ansa‐Arene Ligands: Effects on the Polymerization of Isobutylene (Chem. Eur. J. 1/2015)
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Martin R. Lichtenthaler Steffen Maurer Robert J. Mangan Florian Stahl Florian Mönkemeyer Julian Hamann Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):471-471
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Exploring the Molecular Structure of Imidazolium–Silica‐Based Nanoparticle Networks by Combining Solid‐State NMR Spectroscopy and First‐Principles Calculations
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Dr. Marie‐Alexandra Neouze Martin Kronstein Dr. Marco Litschauer Dr. Michael Puchberger Dr. Cristina Coelho Prof. Christian Bonhomme Prof. Christel Gervais Dr. Frederik Tielens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):15188-15196
A DFT‐based molecular model for imidazolium–silica‐based nanoparticle networks (INNs) is presented. The INNs were synthesized and characterized by using small‐angle X‐ray scattering (SAXS), NMR spectroscopy, and theoretical ab initio calculations. 11B and 31P HETCOR CP MAS experiments were recorded. Calculated 19F NMR spectroscopy results, combined with the calculated anion–imidazolium (IM) distances, predicted the IM chain density in the INN, which was also confirmed from thermogravimetric analysis/mass spectrometry results. The presence of water molecules trapped between the nanoparticles is also suggested. First considerations on possible π–π stacking between the IM rings are presented. The predicted electronic properties confirm the photoluminescence emissions in the correct spectral domain. 相似文献
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Mario Ulises Delgado‐Jaime Prof. Serena DeBeer Prof. Matthias Bauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(47):15888-15897
Valence‐to‐core X‐ray emission spectroscopy (V2C XES) has been applied to a series of compounds relevant to both homogeneous catalysts and intermediates in heterogeneous reactions, namely [Fe(CO)5], [Fe2(CO)9], [Fe3(CO)12], [Fe(CO)3(cod)] (cod=cyclo‐octadienyl), [Fe2Cp2(CO)4] (Cp=cyclo‐pentadienyl), [Fe2Cp*2(CO)4] (Cp*=tetramethylcyclopentadienyl), and [FeCp(CO)2(thf)][B(ArF)4] (ArF=pentafluorophenyl). DFT calculations of the V2C XES spectra show very good agreement with experiment, which allows for an in depth analysis of the origins of the observed spectral signatures. It is demonstrated that the observed spectral features can be broken down into specific ligand and metal fragment contributions. The relative intensities of the observed features are further explained through a quantitative investigation of the metal 3p and 4p contributions to the spectra. The ability to use V2C XES to separate carbonyl, hydrocarbon, and solvent contributions is highlighted. 相似文献
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Characterization of Paramagnetic Reactive Intermediates: Predicting the NMR Spectra of Iron(IV)–Oxo Complexes by DFT
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Dr. Andrea Borgogno Dr. Federico Rastrelli Prof. Alessandro Bagno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):12960-12970
The relative energies of spin states of several iron(IV)–oxo complexes and related species have been calculated with DFT methods by employing the B3LYP* functional. We show that such calculations can predict the correct ground spin state of FeIV complexes and can then be used to determine the 1H NMR spectra of all spin states; the spectral features are remarkably different, hence calculated paramagnetic 1H NMR spectra can be used to support the structure elucidation of numerous paramagnetic complexes. Applications to a number of stable and reactive iron(IV)–oxo species are described. 相似文献
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Identification of tert‐Butyl Cations in Zeolite H‐ZSM‐5: Evidence from NMR Spectroscopy and DFT Calculations
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Dr. Weili Dai Prof.Dr. Chuanming Wang Dr. Xianfeng Yi Prof. Dr. Anmin Zheng Prof. Dr. Landong Li Prof. Dr. Guangjun Wu Prof. Dr. Naijia Guan Prof. Dr. Zaiku Xie Dipl.‐Chem. Michael Dyballa Prof. Dr. Michael Hunger 《Angewandte Chemie (International ed. in English)》2015,54(30):8783-8786
Experimental evidence for the presence of tert‐butyl cations, which are important intermediates in acid‐catalyzed heterogeneous reactions, on solid acids has still not been provided to date. By combining density functional theory (DFT) calculations with 1H/13C magic‐angle‐spinning NMR spectroscopy, the tert‐butyl cation was successfully identified on zeolite H‐ZSM‐5 upon conversion of isobutene by capturing this intermediate with ammonia. 相似文献