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1.
Umie F.M. Haziz Rosenani A. Haque Shun-Ze Zhan Hassan H. Abdallah Mohd R. Razali 《应用有机金属化学》2020,34(10):e5818
The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, 1H- and 13C-NMR data. The 13C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]2·2PF6 is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λem = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm. 相似文献
2.
《Tetrahedron letters》2019,60(24):1582-1586
Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred. 相似文献
3.
Junhua Chen 《Journal of organometallic chemistry》2006,691(3):470-474
Four novel hexadentate imidazolium salts were synthesized from hexakis(bromomethyl)benzene and 1-substituted imidazole. The arylation of aldehydes with arylboronic acids was effected conveniently and in high yields by a catalyst system generated in situ from these hexadentate imidazolium salts, [Rh(COD)Cl]2 and a base. 相似文献
4.
Georg Süss-Fink Ulf Bodensieck Lisa Hoferkamp Gerd Rheinwald Helen Stoeckli-Evans 《Journal of Cluster Science》1992,3(4):469-478
The reaction of trirutheniumdodecacarbonyl with various thioureas was found to give, depending upon the substituents and the reaction conditions, a large variety of tri-, tetra-, penta-, and hexanuclear ruthenium clusters. The ligand systems observed in the products are derived from the thioureas employed; the fragmentation of the thiourea molecules involve N-H, C-S, C-H, and C-N activation processes. 相似文献
5.
Adriana Tudose 《Tetrahedron letters》2006,47(48):8529-8533
Simple catalysts formed in situ from palladium acetate and a variety of imidazolium and imidazolinium carboxylates and dithiocarboxylates have been screened in the coupling of aryl halides with trans-2-phenylvinylboronic acid. Imidazol(in)ium carboxylates show an excellent activity, which compares to that displayed by the parent imidazol(in)ium chlorides, whereas imidazol(in)ium dithiocarboxylates are poorly efficient. Interestingly, the base employed exerts a profound influence on the trans/cis stereochemistry of the coupling product. 相似文献
6.
7.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):303-313
The reaction of electron‐deficient alkenes with alkoxyalkynyl Fischer carbene complexes (FCCs) represents a straightforward route to a new type of captodative (donor–acceptor) alkynylcyclopropanes, which have been prepared in moderate to high yields and in a diastereoselective manner. Some studies regarding the employment of additives to facilitate the recovery of the metal moiety after the reaction are also described. Finally, the first example of a cyclopropanation reaction through employing Fischer carbene complexes under microwave irradiation is presented; this method proved to be an advantageous alternative to the thermal reaction. 相似文献
8.
Xiu Hui Lu Hai Bin Yu Wei Rong Wu Yue Hua Xu 《International journal of quantum chemistry》2007,107(2):451-457
Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
9.
New, sterically demanding 1,3-dialkyl-3,4,5,6-tetrahydropyrimidinium salts (2) as NHC precursors have been synthesized and characterized. These salts, in combination with palladium acetate, provided active catalysts for the cross-coupling of aryl chlorides and bromides under mild conditions. The catalytic system was applied to the Heck, Suzuki and benzaldehyde (Kumada) coupling reactions. Catalyst activity was found to be influenced by the presence of a methoxy group on the ring of the p-position of benzyl substituent of the ligand precursor. 相似文献
10.
Rüdiger Beckhaus 《Angewandte Chemie (International ed. in English)》1997,36(7):686-713
The relation of thermodynamic stability and kinetic lability of σ-organometallic compounds of transition metals, together with an improved understanding of the subtle interactions between central metal, ligands, and substrates, has increased the chemist's ability to plan organometallic syntheses. This article presents new results on intermediary and isolable synthetic building blocks incorporating metal–ligand multiple bonds of electron-deficient transition metals; the main emphasis will be placed on compounds with titanium–carbon double bonds. This particular class of compounds is mainly generated by H-transfer reactions starting from readily accessible alkyl and alkenyl derivatives. The preparative use of [L2Ti(CHR2)R′] derivatives as sources for [L2Ti?CR2] intermediates will be discussed, as well as the nature of these intermediates. Application of the same approach to vinyltitanium compounds [L2Ti(CH?CH2)R] opens up an access to a short-lived metallaallene derivative [L2Ti?C?CH2] of an electron-deficient transition metal. The reactivity of these synthetic building blocks is mainly characterized by the nucleophilic properties of the α-C atoms as well as by the spatial orientation of the π-bonding planes. Numerous cycloaddition products with unsaturated substrates could be isolated and characterized for the first time by using [L2Ti?C?CH2] intermediates. Hence it is possible to compare the properties of a multitude of metallacyclic ring systems with those obtained from “Tebbe–Grubbs chemistry”, and in this context, the dependence of the properties of metallacyclic four-membered rings on the substitution pattern is discussed. This class of compounds includes the metallaoxetanes, which have been obtained for the first time by the cycloaddition of the [CpTi?C?CH2] intermediate with cumulenes and metal carbonyls. The differing cycloreversion behavior of these metallaoxetanes enables the differentiation of species exhibiting classical and nonclassical reactivity. The number and position of the exocyclic double bonds are the determining factors of the reactivity of the formed metallacycles. The discussion of the products obtained from titanium methylene and vinylidene building blocks is an up-to-date report on the formation and applications of carbene complexes and carbene intermediates of group 4 metals. 相似文献