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The diverse mechanisms for the oxidative addition of C-Br bonds to Pd(PR3) and Pd(PR3)2 complexes.
Dalton Trans 2019; 48(43):16242-16248DT

Abstract

The reaction between bromobenzene and palladium(0) complexes leading to a palladium(ii) complex containing bromide and phenyl ligands is studied computationally with DFT methods. Three different mechanisms are considered: concerted, nucleophilic substitution and radical. A systematic analysis is carried out on the effect on each of these mechanisms of a number of variables: the identity of the phosphine (PF3, PH3, PMe3 or PPh3), the nature of the solvent (vacuum, tetrahydrofuran, dimethylformamide or water) and the number of phosphine ligands (mono- or bis-phosphine). The concerted and nucleophilic substitution mechanisms are competitive in many cases, the identity of the preferred one depending on a combination of factors. Additional calculations with bromomethane, bromoethylene and bromoethane are carried out in selected cases for further clarification.

Authors+Show Affiliations

Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Avgda. Països Catalans, 16, 43007 Tarragona, Catalonia, Spain. fmaseras@iciq.es and Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, c/Marcel·lí Domingo s/n, 43007 Tarragona, Catalonia, Spain.Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Avgda. Països Catalans, 16, 43007 Tarragona, Catalonia, Spain. fmaseras@iciq.es and Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia, Spain.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31599918

Citation

Besora, Maria, and Feliu Maseras. "The Diverse Mechanisms for the Oxidative Addition of C-Br Bonds to Pd(PR3) and Pd(PR3)2 Complexes." Dalton Transactions (Cambridge, England : 2003), vol. 48, no. 43, 2019, pp. 16242-16248.
Besora M, Maseras F. The diverse mechanisms for the oxidative addition of C-Br bonds to Pd(PR3) and Pd(PR3)2 complexes. Dalton Trans. 2019;48(43):16242-16248.
Besora, M., & Maseras, F. (2019). The diverse mechanisms for the oxidative addition of C-Br bonds to Pd(PR3) and Pd(PR3)2 complexes. Dalton Transactions (Cambridge, England : 2003), 48(43), pp. 16242-16248. doi:10.1039/c9dt03155c.
Besora M, Maseras F. The Diverse Mechanisms for the Oxidative Addition of C-Br Bonds to Pd(PR3) and Pd(PR3)2 Complexes. Dalton Trans. 2019 Nov 21;48(43):16242-16248. PubMed PMID: 31599918.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - The diverse mechanisms for the oxidative addition of C-Br bonds to Pd(PR3) and Pd(PR3)2 complexes. AU - Besora,Maria, AU - Maseras,Feliu, Y1 - 2019/10/10/ PY - 2019/10/11/pubmed PY - 2019/10/11/medline PY - 2019/10/11/entrez SP - 16242 EP - 16248 JF - Dalton transactions (Cambridge, England : 2003) JO - Dalton Trans VL - 48 IS - 43 N2 - The reaction between bromobenzene and palladium(0) complexes leading to a palladium(ii) complex containing bromide and phenyl ligands is studied computationally with DFT methods. Three different mechanisms are considered: concerted, nucleophilic substitution and radical. A systematic analysis is carried out on the effect on each of these mechanisms of a number of variables: the identity of the phosphine (PF3, PH3, PMe3 or PPh3), the nature of the solvent (vacuum, tetrahydrofuran, dimethylformamide or water) and the number of phosphine ligands (mono- or bis-phosphine). The concerted and nucleophilic substitution mechanisms are competitive in many cases, the identity of the preferred one depending on a combination of factors. Additional calculations with bromomethane, bromoethylene and bromoethane are carried out in selected cases for further clarification. SN - 1477-9234 UR - https://www.unboundmedicine.com/medline/citation/31599918/The_diverse_mechanisms_for_the_oxidative_addition_of_C-Br_bonds_to_Pd(PR3)_and_Pd(PR3)2_complexes L2 - https://doi.org/10.1039/c9dt03155c DB - PRIME DP - Unbound Medicine ER -