Stable Ketenyl Anions via Ligand Exchange at an Anionic Carbon as Powerful Synthons

Wei, Rui1,2; Wang, Xin-Feng1,2; Ruiz, David A. A.1,2; Liu, Liu Leo1,2

2023-03-01

10.1002/anie.202219211

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

Under an atmosphere of carbon monoxide (CO), a (phosphino)diazomethyl anion salt [[P]-CN2][K(18-C-6)(THF)] (1) ([P]=[(CH2)(NDipp)](2)P; 18-C-6=18-crown-6; Dipp=2,6-diisopropylphenyl) undergoes a facile N-2/CO exchange reaction giving the (phosphino)ketenyl anion salt [[P]-CCO][K(18-C-6)] (2). Oxidation of 2 with elemental Se affords the (selenophosphoryl)ketenyl anion salt [P](Se)-CCO][K(18-C-6)] (3). These ketenyl anions feature a strongly bent geometry at the P-bound carbon and this carbon atom is highly nucleophilic. The electronic structure of the ketenyl anion [[P]-CCO](-) of 2 is examined by theoretical studies. Reactivity investigations demonstrate 2 as a versatile synthon for derivatives of ketene, enolate, acrylate and acrylimidate moieties.

Ketene Ketenyl Anion Ligand Exchange Carbyne Anion Main Group Element

SCI ; EI

英语

NI期刊 ; NI论文

第一 ; 通讯

National Natural Science Foundation of China["22271132","22101114"] ; Shenzhen Science and Technology Innovation Program[JCYJ20220530114806015] ; Guangdong Innovation & Entrepreneurial Research Team Program[2021ZT09C278] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:000942826200001

WILEY-V C H VERLAG GMBH

20231013674102

Carbon monoxide ; Crown ethers ; Electronic structure ; Ligands

Physical Chemistry:801.4 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China

Wei, Rui,Wang, Xin-Feng,Ruiz, David A. A.,et al. Stable Ketenyl Anions via Ligand Exchange at an Anionic Carbon as Powerful Synthons[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2023,62(15).

Wei, Rui,Wang, Xin-Feng,Ruiz, David A. A.,&Liu, Liu Leo.(2023).Stable Ketenyl Anions via Ligand Exchange at an Anionic Carbon as Powerful Synthons.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,62(15).

Wei, Rui,et al."Stable Ketenyl Anions via Ligand Exchange at an Anionic Carbon as Powerful Synthons".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 62.15(2023).