期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 894, 期 -, 页码 61-66出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2019.05.006
关键词
Palladacycles; Insertion reactions; Isocyanides; P-ylide; Iminoacyl complexes
资金
- Spanish Ministerio de Economia y Competitividad [CTQ2015-69568-P]
- FEDER
- Fundacion Seneca [19890/GERM/15]
The synthesis of the previously reported complexes [Pd{(C,C-CHCO2R)(2)PPh2}(mu-Cl)](2) (R = Me (1), Et (2)) has been considerably improved by reacting the phosphonium salts [Ph2P(CH2CO2R)(2)]Cl with Pd(OAc)(2). Complexes 1 and 2 react with isocyanides R'NC (R' = C6H4Me2-2,6 (Xy), C6H4I-2 and Bu-t) to give complexes of the type [Pd{C,C-{C(CO2R) = C(NHR')}(CHCO2R)}PPh2}Cl(CNR')], resulting from the insertion of the unsaturated molecule in one of their Pd-C bonds and the hydrogen transfer from the methine CH to the iminobenzoyl nitrogen. These are the first insertion reactions observed in the Pd-C bond of a P-ylide complex. The crystal structure of the complex [Pd{C,C-{C(CO2Me)=C(NHXy)}(CHCO2Me)}PPh2}Cl(CNXy)] (3) is reported. (c) 2019 Elsevier B.V. All rights reserved.
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