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1.
Vjacheslav V. Zuev Dimitry A. de Vekki 《Phosphorus, sulfur, and silicon and the related elements》2013,188(9):2071-2083
The hydrosilylation of a range of para-substituted acetophenones XC6H4COCH3 (X = H, Me, MeO, F, Cl, NO2) with 1,1,3,3-tetramethyl disiloxane mediated by complexes of rhodium (I) and platinum (II) was investigated. The complexes of platinum (II) are less effective than complexes of rhodium (I), but display greater selectivity. Six 1-(1′-arylethoxy)-1,1,3,3-tetramethyl disiloxanes have been synthesized by hydrosilylation using several coupling catalysts. 相似文献
2.
D. A. de Vekki V. A. Ol'sheev V. N. Spevak N. K. Skvortsov 《Russian Journal of General Chemistry》2001,71(12):1912-1923
The rate of addition of MeSiH(OSiMe3)2, Me2SiHOSiMe3, and (Me2SiH)2O to vinylsiloxanes ViMeSi(OSiMe3)2, ViMe2SiOSiMe3, and (ViMe2Si)2O in the presence of square-planar platinum complexes [Pt(LL')X2] (where L and L' are neutral ligands, and X is an anionic ligand) decreases in the following series of L and L': Ph3PS > MeS(O)Tol-p > MeCOD > CH2ÍCH2 COD > Et2SO > Et2S > Me2SO 2-aminopyridine > Py > 2-methylpyridine. Variation of X, the ligands L and L' remaining unchanged, leads to decrease in the reaction rate in the series: C2O4
2
- > NO3
- > Cl- Br-. Mixed-ligand complexes like (-)-[Pt(MeSOTol-p)PyCl2] having a cis structure are more efficient catalysts then the corresponding trans isomers in the hydrosilylation of siloxanes. Reactions of sulfoxide platinum(II) complexes with vinylsiloxanes and silicon hydrides result in isomerization of the metal complex and dissociation of the sulfoxide; bis-sulfoxide complexes undergo deoxygenation of the sulfoxide ligand with formation of colloidal platinum. It was presumed that the active form of the catalyst is its trans isomer; it reacts with silicon hydride, leading to replacement of the sulfoxide ligand in the inner sphere of platinum(II) complex. The reactivity of silicon hydrides toward vinylsiloxanes in the presence of sulfoxide platinum(II) complexes decreases in the series (Me2SiH)2O > Me2SiHOSiMe3 > MeHSi(OSiMe3)2, and the vinylsiloxanes form the following reactivity series: ViMe2SiOSiMe3 > ViMeSi(OSiMe3)2 > (ViSiMe2)2O. These series conform to increase of the positive charge on the silicon atom and decrease in steric hindrance created by the substituents thereon. 相似文献
3.
Angélique Kergreis Dr. Rianne M. Lord Dr. Sarah J. Pike 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):14938-14946
A series of cyclometallated mono- and di-nuclear platinum(II) complexes and the parent organic ligand, 2,6-diphenylpyridine 1 (HC^N^CH), have been synthesized and characterized. This library of compounds includes [(C^N^C)PtII( L )] ( L =dimethylsulfoxide (DMSO) 2 and triphenylphosphine (PPh3) 3 ) and [((C^N^C)PtII)2( L‘ )] (where L‘ =N-heterocycles (pyrazine (pyr) 4 , 4,4‘-bipyridine (4,4‘-bipy) 5 or diphosphine (1,4-bis(diphenylphosphino)butane (dppb) 6 ). Their cytotoxicity was assessed against four cancerous cell lines and one normal cell line, with results highlighting significantly increased antiproliferative activity for the dinuclear complexes ( 4 – 6 ), when compared to the mononucleated species ( 2 and 3 ). Complex 6 is the most promising candidate, displaying very high selectivity towards cancerous cells, with selectivity index (SI) values >29.5 (A2780) and >11.2 (A2780cisR), and outperforming cisplatin by >4-fold and >18-fold, respectively. 相似文献
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首次合成了巯甲基化交联聚苯乙烯-铂络合物,将其用于催化不同结构的碳碳不饱和化合物与甲基二氯硅烷的加成反应,结果表明,该催化剂对乙炔、苯乙烯、苯乙炔、三烷基乙烯基硅烷等化合物具有很高的催化活性,对丙烯酸丁酯的催化活性显著降低,对甲基丙烯酸甲酯则无催化活性,该催化剂用于苯乙烯的硅氢加成反应,可重复使用20次,而且回收再用非常方便。 相似文献
5.
Hydrosilylation of allyl ethyl, allyl butyl, allyl glycidyl, allyl benzyl, and allyl phenyl ethers by 1,1,3,3-tetramethyldisiloxane in the presence of supported sulfur-containing platinum(II) complexes with the general formula [{SiO2}O2Si(Me)(CH2)3SR]2PtCl2 (R = Bu, Hex, Bn; {SiO2} is silica surface) and side processes have been studied. 相似文献
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Catalytic properties of thermo- and photoactivated platinum complexes [Pt(R2R'X)2Cl2] (X = P, R = Me, R' = Ph; X = P, As, Sb, R = R' = Ph or Bu) in hydrosilylation of vinylsiloxanes with hydrosiloxanes were studied. The neutral ligands were ranked in terms of their effect on the activity of the catalysts. A mechanism of hydrosilylation was proposed. 相似文献
8.
Cedric Groß Andreas Omlor Tobias Grimm Benjamin Oelkers Yu Sun Volker Schünemann Werner R. Thiel 《无机化学与普通化学杂志》2020,646(13):968-977
Enantiomerically pure, C2-symmetric 2,6-bis(pyrazol-3-yl) pyridine ligands were obtained by treatment of diethyl-2,6-pyridinedicarbonate with (1R,4R)-(+)-camphor in the presence of NaH followed by ring closure with hydrazine. After twofold N-alkylation at the pyrazole rings, the addition of iron(II) chloride led to the according pentacoordinate dichloridoiron(II) complexes. All intermediates of the ligand synthesis, the ligands bearing NCH3 and NCH2C6H5 groups and the derived iron(II) complexes were structurally characterized by means of X-ray structure analysis. In-situ reaction with iron(II) carboxylates resulted in the formation of iron(II) carboxylate complexes, which turned out to be highly active in the hydrosilylation of acetophenone. However, even at room temperature, the enantiomeric excess of the product 1-phenylethanol is poor. 57Fe Mössbauer spectroscopy gave an insight into the species formed during catalysis. 相似文献
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When the platinum(II) and palladium(II) salts interact with ligands such as cystamine-(mercamine) HSCH2CH2NH2 and 2-mercaptoethanol HSCH2CH2OH under certain conditions, polynuclear complexes of the compositions are obtained: [Pt6(SCH2CH2NH2)8]Cl4. 5H2O and [Pd6(SCH2CH2OH)8]Cl4. In a comparative study of the IR and X-ray spectra of synthesized complexes and ligands, as well as the results of X-ray diffraction studies, it was established that sulfur atoms of 2-mercaptoethanol occupy a bridge position with a mixed coordination of ligands in the palladium complex. In the platinum(II) complex bidentate coordination of ligands is realized through sulfur and nitrogen atoms. 相似文献
13.
Platinum(II) cyanophosphine complexes PtL2Cl2, where L = P(CN)3, PhP(CN)2, or Ph2PCN, were synthesized. Their properties and mode of coordination were examined. 相似文献
14.
Egor M. Baranovskii Victoria V. Khistiaeva Konstantin V. Deriabin Stanislav K. Petrovskii Igor O. Koshevoy Ilya E. Kolesnikov Elena V. Grachova Regina M. Islamova 《Molecules (Basel, Switzerland)》2021,26(22)
This study focuses on the synthesis of hybrid luminescent polysiloxanes and silicone rubbers grafted by organometallic rhenium(I) complexes using Cu(I)-catalyzed azido-alkyne cycloaddition (CuAAC). The design of the rhenium(I) complexes includes using a diimine ligand to create an MLCT luminescent center and the introduction of a triple C≡C bond on the periphery of the ligand environment to provide click-reaction capability. Poly(3-azidopropylmethylsiloxane-co-dimethylsiloxane) (N3-PDMS) was synthesized for incorporation of azide function in polysiloxane chain. [Re(CO)3(MeCN)(5-(4-ethynylphenyl)-2,2′-bipyridine)]OTf (Re1) luminescent complex was used to prepare a luminescent copolymer with N3-PDMS (Re1-PDMS), while [Re(CO)3Cl(5,5′-diethynyl-2,2′-bipyridine)] (Re2) was used as a luminescent cross-linking agent of N3-PDMS to obtain luminescent silicone rubber (Re2-PDMS). The examination of photophysical properties of the hybrid polymer materials obtained show that emission profile of Re(I) moiety remains unchanged and metallocenter allows to control the creation of polysiloxane-based materials with specified properties. 相似文献
15.
Burlov A. S. Mashchenko S. A. Vlasenko V. G. Kiskin M. A. Nikolaevskii S. A. Korshunova E. V. 《Russian Journal of Coordination Chemistry》2019,45(11):782-787
Russian Journal of Coordination Chemistry - New Ni(II) and Pd(II) complexes (Ia and Ib) are synthesized on the basis of the azomethine compound... 相似文献
16.
Lisa Gourdon-Grünewaldt Marija Bakija Lara Wild Berislav Perić Gilles Gasser Srećko I. Kirin Kevin Cariou 《Helvetica chimica acta》2023,106(8):e202300078
With the aim of achieving bioorthogonal intracellular catalysis, a library of platinum(II) complexes was synthesized. Their non-toxicity to living cells was demonstrated and their catalytic activity was evaluated on a cyclization reaction leading to a highly fluorescent coumarin. None of the platinum complexes showed any catalytic activity for coumarin synthesis. Still, we demonstrated that the silver salt AgSbF6 commonly used to ‘activate’ metal catalysts by removing a chloride is a very efficient catalyst for the studied intramolecular cyclization reaction. 相似文献
17.
The synthesis of a mononuclear Rh(III) complex, as a representative example of a series of related species, containing two cyclometallating ligands ppy (2-phenylpyridine) and one diimine bpy (2,2′-bipyridine) from a binuclear Cl-bridged compound is described. The absorption spectrum shows a maximum at 364 nm (ε = 7000), with a very weak shoulder (ε = 10) at 454 nm. This band is tentatively assigned to a metal-to-ligand charge-transfer transition. A reversible, one-electron reduction appears in the cyclic voltammogram at E1/2 = ?1.41 V (vs. NHE) and a irreversible oxydation at Ep = + 1.1 V. A detailed NMR analysis including 13C-NMR, NOE, SFORD as well as deuteration of the bpy ligand indicates the formation of only one isomer, having a C2 axis, bisecting the bpy ligand, with the two carbon ligands in cis-position. 103Rh, 13C and 103Rh,H couplings are observed. 相似文献
18.
D. A. de Vekki V. M. Uvarov N. K. Skvortsov 《Russian Journal of General Chemistry》2005,75(3):321-324
Preparation of platinum cyclooctadiene complexes under photoirradiation was studied, and the reaction mechanism was suggested.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 3, 2005, pp. 353–356.Original Russian Text Copyright © 2005 by de Vekki, Uvarov, Skvortsov. 相似文献
19.
《Journal of Coordination Chemistry》2012,65(4):349-357
Abstract The reaction of platinum(II) halides with stoichiometric amounts of either dimethyl sulfoxide (DMSO) or thiocarbamic ester (L) in acetone yields the complexes cis-[Pt(L)(DMSO)X2], where L α MTC (EtOSCNHMe), ETC (EtOSCNHEt) or TC (EtOSCNH2) and X α Cl or Br. The compounds have been isolated and characterized by elemental analysis and by infrared and nmr (1H and 13C) spectroscopy. Either dimethyl sulfoxide or thiocarbamic ester coordinate through the sulphur atom. In the MTC and ETC adducts the planar ligand molecule is present in the isomeric form bearing the N-alkyl group in an anti position with respect to the thiocarbonyl group. 相似文献
20.
《Journal of Coordination Chemistry》2012,65(6):659-665
A series of novel trans-mixed diamine platinum(II) and platinum(IV) complexes of type trans-[PtII(R-NH2)(R'-NH2)Cl2] and trans -[PtIV(R-NH2)(R'-NH2)Cl4] (where R-NH2 = ethylamine or butylamine and R'-NH2 = methylamine, propylamine, isopropylamine, pentylamine, or hexylamine) was synthesized and characterized using elemental analysis and infrared and 195Pt nuclear magnetic resonance spectroscopic techniques. 相似文献