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• W2013277728 abstract "The structure and reactivity of various bis-allylpalladium complexes occurring as catalytic intermediates in important synthetic transformations have been studied by applying density functional theory at the B3PW91(DZ + P) level. It was found that n1,n3 coordinated bis-allylpalladium complexes are readily formed from the corresponding n3,n3 complexes, especially in the presence of pi-acceptor phosphine ligands. The theoretical calculations indicate dsigma-->pi type hyperconjugative interactions occurring in the n1-coordinated allyl moiety of the n3,n3 coordinated complexes. These hyperconjugative interactions influence the structure of the complexes and dramatically increase the reactivity of the double bond in the n1-moiety. The DFT results indicate a remarkably low activation barrier for the electrophilic attack on the n1-allyl functionality. In bridged n1,n3 complexes, the electrophilic attack occurs with a very high regioselectivity, which can be explained on the basis of d-pi type hyperconjugative interactions." @default.
• W2013277728 created "2016-06-24" @default.
• W2013277728 creator A5088269285 @default.
• W2013277728 date "2000-12-01" @default.
• W2013277728 modified "2023-10-16" @default.
• W2013277728 title "Umpolung of the Allylpalladium Reactivity: Mechanism and Regioselectivity of the Electrophilic Attack on Bis-Allylpalladium Complexes Formed in Palladium-Catalyzed Transformations" @default.
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• W2013277728 doi "https://doi.org/10.1002/1521-3765(20001201)6:23<4413::aid-chem4413>3.3.co;2-i" @default.
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