Preparation, Structure, and Reactions of Trifluoroacetimidoyl Palladium(II) Complexes

被引:15
|
作者
Amii, Hideki [1 ,2 ]
Kageyama, Katsuhiko [1 ]
Kishikawa, Yosuke [1 ]
Hosokawa, Tsuyoshi [1 ]
Morioka, Ryo [2 ]
Katagiri, Toshimasa [1 ]
Uneyama, Kenji [1 ]
机构
[1] Okayama Univ, Fac Engn, Dept Appl Chem, Okayama 7008530, Japan
[2] Gunma Univ, Grad Sch Engn, Dept Chem & Chem Biol, Kiryu, Gunma 3768515, Japan
关键词
TRANSITION-METAL-COMPLEXES; CROSS-COUPLING REACTIONS; COPPER-CATALYZED TRIFLUOROMETHYLATION; ISOCYANIDE INSERTION REACTIONS; F REDUCTIVE ELIMINATION; PUSH-PULL CARBENES; IMIDOYL CHLORIDES; MEDIATED TRIFLUOROMETHYLATION; ORGANOMETALLIC COMPOUNDS; OXIDATIVE ADDITION;
D O I
10.1021/om201021b
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Trifluoroacetimidoyl metal complexes are useful intermediates for the selective synthesis of organofluorine compounds. Herein, we report preparations, structures, and reactions of fluorinated imidoyl palladium complexes. Oxidative addition of trifluoroacetimidoyl halides to Pd(PPh3)(4) afforded quantitatively the imidoyl palladium(II) complexes with phosphine ligands. The reaction of trifluoroacetimidoyl iodides with Pd-2(dba)(3) provided the phosphine-free imidoyl palladium complex in high yields. The X-ray crystal structure analysis of the phosphine-free complex [Pd(mu-I){mu-C(CF3)=N(PMP)}](4) revealed a cyclic tetranuclear structure containing the imidoyl and iodo bridges. The generation of aminotrifluoromethylcarbene equivalents by protonation or electrophilic alkylation of imidoyl palladium(II) complexes is discussed.
引用
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页码:1281 / 1286
页数:6
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