Complexes of the composition trans-[Pd(L)2(OAc)2] have been postulated as intermediates during cyclopalladation. The first structural characterization of such a precursor has now been achieved and its role in the reaction sequence has been established. Diacetato-kappa2O-bis[(S)-1-(4-fluorophenyl)ethylamine-kappaN]palladium(II), [Pd(O2CMe)2(4-FC6H3CHMeNH2)2] or [Pd(C2H3O2)2(C8H10FN)2], (I), was obtained from palladium(II) acetate and (S)-NH2CHMeC6H3F-4 in a 1:2 molar ratio. The intermediate was then reacted with additional palladium(II) acetate to give the acetate-bridged dinuclear complex di-mu-acetato-kappa4O:O'-bis[[(S)-2-(1-aminoethyl)-5-fluorophenyl-kappa2C1,N]palladium(II)] benzene hemisolvate, [Pd(4-FC6H3CHMeNH2)2(mu-O2CMe)]2.0.5C6H6 or [Pd2(C8H9FN)2(C2H3O2)2].0.5C6H6, (II).
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http://dx.doi.org/10.1107/S0108270104010856 | DOI Listing |
J Org Chem
January 2025
Department of Chemistry, Illinois State University, Normal, Illinois 61790-4160, United States.
Acid catalyzed condensation of -alkyltripyrranes with trialdehydes derived from 1,3-cyclopentadiene or methyl-1,3-cyclopentadiene, followed by oxidation with aqueous ferric chloride solutions, gave 23-alkyl-21-carbaporphyrin-2-carbaldehydes in 22-27% yield together with weakly aromatic oxycarbaporphyrins. The carbaporphyrins reacted with palladium(II) acetate or nickel(II) acetate to give organometallic complexes but in both cases alkyl group migration took place to generate 21-alkyl derivatives. Although this type of reactivity had been observed previously for palladium complexes, this is the first time the phenomenon has been seen in nickel(II) carbaporphyrins.
View Article and Find Full Text PDFACS Omega
September 2024
Departamento de Física de la Materia Condensada C-III, and Instituto Universitario de Ciencia de Materiales "Nicolás Cabrera", Universidad Autónoma de Madrid, E-28049 Madrid, Spain.
The present work provides insight into the effect of connectivity within isomeric 1,2-bis(2-pyridylethynyl)benzene (bpb) palladium complexes on their electron transmission properties within gold|single-molecule|gold junctions. The ligands 2,2'-((4,5-bis(hexyloxy)-1,2-phenylene)bis(ethyne-2,1-diyl))bis(4-(methylthio)pyridine) ( ) and 6,6'-((4,5-bis(hexyloxy)-1,2-phenylene)bis(ethyne-2,1-diyl))bis(3-(methylthio)pyridine) ( ) were synthesized and coordinated with PdCl to give the -Pd( )Cl complexes. X-ray photoelectron spectroscopy (XPS) measurements shed light on the contacting modes of the molecules in the junctions.
View Article and Find Full Text PDFDalton Trans
November 2022
Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Collaborative Innovation Centre of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, China.
A palladium(II) hydride complex supported by a benzene-based PNCNP pincer ligand, [2,6-(BuPNH)CH]PdH (1), has been synthesized two different routes: the reaction of the corresponding chloride complex with LiAlH and the reaction of the corresponding nitrate complex with KOCH. Complex 1 exhibits strong deprotonating ability and versatile catalytic activity. Acetamide can be readily deprotonated by complex 1 to form the corresponding acetamido complex, [2,6-(BuPNH)CH]PdNHC(O)CH, in high yield.
View Article and Find Full Text PDFFront Chem
April 2019
Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La Trobe University, Melbourne, VIC, Australia.
A modular stepwise synthetic method has been developed for the preperation of -imidazolium macrocycles. Initially a series of three (imidazolylmethyl)benzene precursors were alkylated with 1,2-dibromoethane to produce the corresponding -bromoethylimidazolium bromide salts. In the second step the -bromoethylimidazolium bromide salts were reacted with selected (imidazolylmethyl)benzene molecules to produce a series of two symmetrical and three asymmetrical -imidazolium macrocycles.
View Article and Find Full Text PDFActa Crystallogr C Struct Chem
May 2019
Université de Toulouse, CNRS, INPT, UPS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France.
The self-assembly of ditopic bis(1H-imidazol-1-yl)benzene ligands (L) and the complex (2,2'-bipyridyl-κN,N')bis(nitrato-κO)palladium(II) affords the supramolecular coordination complex tris[μ-bis(1H-imidazol-1-yl)benzene-κN:N]-triangulo-tris[(2,2'-bipyridyl-κN,N')palladium(II)] hexakis(hexafluoridophosphate) acetonitrile heptasolvate, [Pd(CHN)(CHN)](PF)·7CHCN, 2. The structure of 2 was characterized in acetonitrile-d by H/C NMR spectroscopy and a DOSY experiment. The trimeric nature of supramolecular coordination complex 2 in solution was ascertained by cold spray ionization mass spectrometry (CSI-MS) and confirmed in the solid state by X-ray structure analysis.
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