Synthesis and properties of (η3-1-methylallyl)palladium(II) formates as models of intermediates in the palladium-catalyzed reductive cleavage of allylic carboxylates and carbonates with formic acid

Masato Oshima*, Toshiaki Sakamoto, Yooichiroh Maruyama, Fumiyuki Ozawa, Isao Shimizu, Akio Yamamoto

*この研究の対応する著者

研究成果: Article査読

16 被引用数 (Scopus)

抄録

In order to gain insight into the mechanism of the regioselective formation of alkenes in the palladium-catalyzed reductive cleavage of allylic carboxylates or carbonates with formic acid, two types of (η3-1- methylallyl)palladium formates (P1 and P2 types) have been prepared as simple models of catalytic intermediates. The P1 type is a neutral complex coordinated with one tertiary phosphine ligand and a formato ligand: [Pd(η3-MeCHCHCH2)(O2CH)(L)] (L = PMePh2, PMe2Ph, PMe3, P(o-tolyl)3); the P2 type is a cationic complex bearing two tertiary phosphine ligands and a formate counter anion: [Pd(η3-MeCHCHCH2)L2]+CO2H- (L = PMePh2, PMe2Ph, PMe3). The structures and dynamic behavior of the complexes in solution have been examined in detail by NMR spectroscopy. Studies on the thermolysis of the P1 and P2- type complexes have clearly provided the following mechanistic viewpoints: (1) 1-butene and 2-butene are formed from the PI species; (2) butadiene is liberated from the P2 species; (3) the ratio of 1-butene to 2-butene increases as the bulkiness of phosphine ligand increases. A mechanism involving two geometrical isomers of [Pd(η3- MeCHCHCH2)(H)(L)], which are formed by decarboxylation of the P1-type complexes, has been proposed for the formation of butenes.

本文言語English
ページ(範囲)453-464
ページ数12
ジャーナルBulletin of the Chemical Society of Japan
73
2
DOI
出版ステータスPublished - 2000 2月

ASJC Scopus subject areas

  • 化学 (全般)

フィンガープリント

「Synthesis and properties of (η3-1-methylallyl)palladium(II) formates as models of intermediates in the palladium-catalyzed reductive cleavage of allylic carboxylates and carbonates with formic acid」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

引用スタイル