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91.
The title compound has been synthesized and the kinetic parameters of its aromatization have been measured. In the key-step of the synthesis 3,6-dihydrobenzocyclobutadiene is used, a new and powerful diene that cycloadds along its axis. 相似文献
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The performance of 23 density functionals, including one LDA, four GGAs, three meta-GGAs, three hybrid GGAs, eight hybrid meta-GGAs, and ten double-hybrid functionals, was investigated for the computation of activation energies of various covalent main-group single bonds by four catalysts: Pd, PdCl−, PdCl2, and Ni (all in the singlet state). A reactant complex, the barrier, and reaction energy were considered, leading to 164 energy data points for statistical analysis. Extended Gaussian AO basis sets were used in all calculations. The best functional for the complete benchmark set relative to estimated CCSD(T)/CBS reference data is PBE0-D3, with an MAD value of 1.1 kcal mol−1 followed by PW6B95-D3, the double hybrid PWPB95-D3, and B3LYP-D3 (1.9 kcal mol−1 each). The other tested hybrid meta-GGAs perform less well (M06-HF: 7.0 kcal mol−1; M06-2X: 6.3 kcal mol−1; M06: 4.9 kcal mol−1) for the investigated reactions. In the Ni case, some double hybrids show larger errors due to partial breakdown of the perturbative treatment for the correlation energy in cases with difficult electronic structures (partial multi-reference character). Only double hybrids either with very low amounts of perturbative correlation (e.g., PBE0-DH) or that use the opposite-spin correlation component only (e.g., PWPB95) seem to be more robust. We also investigated the effect of the D3 dispersion correction. While the barriers are not affected by this correction, significant and mostly positive results were observed for reaction energies. Furthermore, six very recently proposed double-hybrid functionals were analyzed regarding the influence of the amount of Fock exchange as well as the type of perturbative correlation treatment. According to these results, double hybrids with <50–60 % of exact exchange and ∼30 % perturbative correlation perform best. 相似文献
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Heitmann D Pape T Hepp A Mück-Lichtenfeld C Grimme S Hahn FE 《Journal of the American Chemical Society》2011,133(29):11118-11120
Reaction of the N,N'-diisobutyl-substituted benzannulated N-heterocyclic plumbylene (NHPb) 1 with [Pd(PPh(3))(4)] and [Pt(PPh(3))(4)] gave the complexes [M(NHPb)(PPh(3))(3)] (M = Pd [2], Pt [3]). X-ray diffraction studies of both complexes showed an angle of ~125° between the plumbylene plane and the transition-metal-Pb axis, indicating coordination of the transition metal to the empty π orbital of the plumbylene Pb atom. The experimentally determined metric parameters of complexes [2] and [3] are discussed on the basis of DFT calculations. 相似文献
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Dr. Karel Škoch Dr. Constantin G. Daniliuc Dr. Gerald Kehr Sebastian Ehlert Marcel Müller Prof. Dr. Stefan Grimme Prof. Dr. Gerhard Erker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(47):12104-12114
Attachment of a pair of P-stereogenic mesityl(alkynyl)phosphanyl groups at the 4- and 5-positions of a 9,9-dimethylxanthene framework gave mixtures of the respective rac- and meso-bisphosphanyl diastereoisomers. They slowly epimerized in a thermally induced reaction with Gibbs activation barriers of about 25 kcal mol−1 at room temperature (measured and DFT calculated). The reaction of the meso-mesityl(tert-butylethynyl)phosphanyl derivative with two molar equivalents of Piers′ borane [HB(C6F5)2] led to the formation of the alkylidene-bridged geminal bisphosphane/borane-frustrated Lewis pair system. The compound was obtained enriched (>85 %) in the rac diastereoisomer. With a variety of bifunctional donor substrates, the rac-bis-P/B FLP formed macrocyclic compounds. They were all formally derived from meso-configurated diastereoisomers of the bisphosphanylxanthene backbone. 相似文献
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