Journal ArticleDOI
Direct Access to Palladium(II) Complexes Based on Anionic C,C,C-Phosphonium Ylide Core Pincer Ligand.
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TLDR
In this article, the pincer complex of imidazolium-phosphonium salt [MesIm(CH2)3PPh3](OTf)2 with PdCl2 in the presence of an excess of Cs2CO3 afforded selectively in one step the cationic Pd(II) complex exhibiting an LX2-type NHC-ylide-aryl C,C,C-pincer ligand via formal triple C-H bond activation.Abstract:
The reaction of readily available imidazolium-phosphonium salt [MesIm(CH2)3PPh3](OTf)2 with PdCl2 in the presence of an excess of Cs2CO3 afforded selectively in one step the cationic Pd(II) complex [(C,C,C)Pd(NCMe)](OTf) exhibiting an LX2-type NHC-ylide-aryl C,C,C-pincer ligand via formal triple C-H bond activation. The replacement of labile MeCN in the latter by CNtBu and CO fragments allowed to estimate the overall electronic properties of this phosphonium ylide core pincer scaffold incorporating three different carbon-based donor ends by IR spectroscopy, cyclic voltammetry, and molecular orbital analysis, revealing its significantly higher electron-rich character compared to the structurally close NHC core pincer system with two phosphonium ylide extremities. The pincer complex [(C,C,C)Pd(CO)](OTf) represents a rare example of Pd(II) carbonyl species stable at room temperature and characterized by X-ray diffraction analysis. The treatment of isostructural cationic complexes [(C,C,C)Pd(NCMe)](OTf) and [(C,C,C)Pd(CO)](OTf) with (allyl)MgBr and nBuLi led to the formation of zwitterionic phosphonium organopalladates [(C,C,C)PdBr] and [(C,C,C)Pd(COnBu)], respectively.read more
Citations
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Journal ArticleDOI
Diverse C-Coordination Modes of NHC-Tricyclohexylphosphonium Ylide Ligands in Palladium(II) Complexes
Mustapha El kadiri,Abdelali Chihab,Rachid Taakili,Carine Duhayon,Dmitry A. Valyaev,Yves Canac +5 more
TL;DR: In this paper , the electron-rich pincer complex (C,C, C)PdCl with AgOTf was shown to have a stronger electron-donating character in comparison to the structurally related NHC core pincers bearing +PPh3 extremities.
Journal ArticleDOI
Carbenes and phosphonium ylides: a fruitful association in coordination chemistry.
Dmitry A. Valyaev,Yves Canac +1 more
TL;DR: In this paper, the chemistry of σ-donor carbon-centered carbenes was comprehensively covered from synthesis and fundamental aspects to catalytic applications, and the design of hybrid systems combining these two types of carbon functionalities appeared to be a natural and exciting challenge.
Journal ArticleDOI
Air-Stable Single-Component Pd-Catalysts for Vinyl-Addition Polymerization of Functionalized Norbornenes
Evgeniya V. Bermesheva,E. I. Medentseva,A. P. Khrychikova,Alyona I. Wozniak,M. A. Guseva,Ivan V Nazarov,A. A. Morontsev,G. O. Karpov,Maxim A. Topchiy,Andrey F. Asachenko,Anastasia A. Danshina,Yulia V. Nelyubina,Maxim V. Bermeshev +12 more
TL;DR: In this article , the authors have shown that cationic Pd-complexes with N-heterocyclic carbene ligands (NHC ligands) and weak coordinating anion ligands ([(NHC)Pd(allyl)L]+A−, where allyl is an allyl group, L = CO, CH3CN, CH2Cl2, and A− = SbF6− or BARF−) are highly efficient single-component catalysts for VAP of both norbornene and various substituted norbornenes.
Journal ArticleDOI
Experimental and theoretical insights into trans influence of organo-sulfur and -selenium ligands in 5,6-membered palladium(II) cationic pincer complexes based on iminophosphoranes
Aurora Rodríguez-Álvarez,Cristina E. González-Espinoza,Carla Gabriela Martínez-De-León,Mauricio Carrillo-Tripp,Minhhuy Hô,Jean-Michel Grévy +5 more
TL;DR: Novel iminophosphorane based heterotridentate SNS and SNSe ligands with the general formula MeSC6H4P(Ph2)=NC6H 4ER (ER= SMe 3a, SPh 3b, SeMe 3c, SePh 3d) and their corresponding Pd(II) cationic complexes with tetrafluoroborate were described in this paper .
Journal ArticleDOI
Phosphonium Ylides vs Iminophosphoranes: The Role of the Coordinating Ylidic Atom in cis-[Phosphine-Ylide Rh(CO)2] Complexes.
Ingrid Popovici,Cécile Barthes,Thibault Tannoux,Carine Duhayon,Nicolas Casaretto,Antonio Monari,Audrey Auffrant,Yves Canac +7 more
TL;DR: In this article , the coordination properties of two families of ylides, namely, phosphonium ylide and iminophosphoranes, differently substituted at the ylidic center (CH2- vs NiPr-), have been investigated in structurally related cationic phosphine-ylide Rh(CO)2 complexes obtained from readily available phosphinephosphonium salt precursors derived from an ortho-phenylene bridge.
References
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Journal ArticleDOI
An empirical correction for absorption anisotropy
TL;DR: A least-squares procedure is described for modeling an empirical transmission surface as sampled by multiple symmetry-equivalent and/or azimuth rotation-equ equivalent intensity measurements.
Journal ArticleDOI
SUPERFLIP– a computer program for the solution of crystal structures by charge flipping in arbitrary dimensions
Lukáš Palatinus,Gervais Chapuis +1 more
TL;DR: SUPERFLIP is a computer program that can solve crystal structures from diffraction data using the recently developed charge-flipping algorithm and has been successfully compiled and tested on a variety of operating systems.
Journal ArticleDOI
BYPASS: an effective method for the refinement of crystal structures containing disordered solvent regions
P. van der Sluis,A. L. Spek +1 more
TL;DR: In this article, a method for least squares refinement of the atomic parameters of the ordered part of a crystal structure in the presence of disordered solvent areas is described, and the contribution of the observed contents to the total structure factor is calculated via a discrete Fourier transformation.
Journal ArticleDOI
An overview of N-heterocyclic carbenes
TL;DR: A concise overview of N-heterocyclic carbenes in modern chemistry is provided, summarizing their general properties and uses and highlighting how these features are being exploited in a selection of pioneering recent studies.
Journal ArticleDOI
Hydrogen bond strengths revealed by topological analyses of experimentally observed electron densities
TL;DR: In this article, the topological properties of ρ(r) at the intermolecular critical points of 83 experimentally observed hydrogen bonds [X-H⋯O (X=C,N,O)], using accurate X-ray diffraction experiments, were analyzed.