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Keywords = bis(phosphane) palladium complex

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12 pages, 1320 KB  
Article
Cyclometallated Palladium(II) Complexes: An Approach to the First Dinuclear Bis(iminophosphorane)phosphane-[C,N,S] Metallacycle
by Marcos Rúa-Sueiro, Paula Munín-Cruz, Adolfo Fernández, Juan M. Ortigueira, María Teresa Pereira and José M. Vila
Molecules 2022, 27(20), 7043; https://doi.org/10.3390/molecules27207043 - 19 Oct 2022
Cited by 2 | Viewed by 2006
Abstract
Treatment of bis(iminophosphorane)phosphane ligands 2a2e with Li2PdCl4 gave a set of novel diphosphane-derived complexes bearing two metallacycle rings, each one enclosing a P=N double bond: the unprecedented bis(iminophosphorane)phosphane-[C,N,S] palladacycles. In the case of the ligand derived from bis(diphenylphosphino)methane, [...] Read more.
Treatment of bis(iminophosphorane)phosphane ligands 2a2e with Li2PdCl4 gave a set of novel diphosphane-derived complexes bearing two metallacycle rings, each one enclosing a P=N double bond: the unprecedented bis(iminophosphorane)phosphane-[C,N,S] palladacycles. In the case of the ligand derived from bis(diphenylphosphino)methane, 2a, both the single and the double palladacycle complexes were obtained. Reaction of 3a with bis(diphenylphosphino)ethane did not yield the expected product with the diphosphane bonded to both palladium atoms, but rather the novel coordination compound 5. The crystal structures of 3c and 5 are described. Full article
(This article belongs to the Special Issue Organometallic Complexes: Fundamentals and Applications)
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22 pages, 14122 KB  
Article
New Rigid Polycyclic Bis(phosphane) for Asymmetric Catalysis
by K. Michał Pietrusiewicz, Katarzyna Szwaczko, Barbara Mirosław, Izabela Dybała, Radomir Jasiński and Oleg M. Demchuk
Molecules 2019, 24(3), 571; https://doi.org/10.3390/molecules24030571 - 5 Feb 2019
Cited by 11 | Viewed by 4196
Abstract
A simple, highly efficient synthesis of a series of novel chiral non-racemic rigid tetracyclic phosphorus ligands, applicable in important chemical asymmetric transformations, was performed. In a tandem cross-coupling/C-H bond activation reaction, a well-recognised and readily available ligand (R,R)-NORPHOS was used as the [...] Read more.
A simple, highly efficient synthesis of a series of novel chiral non-racemic rigid tetracyclic phosphorus ligands, applicable in important chemical asymmetric transformations, was performed. In a tandem cross-coupling/C-H bond activation reaction, a well-recognised and readily available ligand (R,R)-NORPHOS was used as the starting material. The palladium complexes of new ligands were obtained and characterised on the example of a crystalline dichloropalladium complex of [(1R,2R,9S,10S,11R,12R)-4-phenyltetracyclo[8.2.1.02,9.03,8]trideca-3,5,7-triene-11,12-diyl]bis(diphenylphosphane). A notably high activity and stereoselectivity of the palladium catalysts based on the new ligands were confirmed in a model asymmetric allylic substitution reaction. Herein, we discuss the geometry of the palladium complexes formed and its impact on the efficiency of the catalysts. A comparison of their geometric features with other bis(phosphane) ligand complexes found in the Cambridge Structural Database and built density functional theory (DFT) commutated models is also presented and rationalised. Full article
(This article belongs to the Special Issue Organophosphorus Chemistry 2018)
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