Releasing Antiaromaticity in Metal-Bridgehead Naphthalene

Tang，Chun1,2; Zhao，Yu2,3; Wu，Jingjing2,3; Chen，Zhixin2; Liu，Liu Leo1; Tan，Yuan Zhi2; Zhu，Jun2,3; Xia，Haiping1,2

2021

10.1021/jacs.1c08106

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

As a fundamental chemical property, aromaticity guides the synthesis of novel structures and materials. Replacing the carbon moieties of aromatic hydrocarbons with transition metal fragments is a promising strategy to synthesize intriguing organometallic counterparts with a similar aromaticity to their organic parents. However, since antiaromaticity will endow compound instability, it is a great challenge to obtain an antiaromatic organometallic counterpart based on such transition metal replacement in aromatic hydrocarbons. Here, we report an efficient aromaticity transformation on aromatic naphthalene through the bridgehead replacement of an osmium fragment, leading to the unprecedented synthesis of metal-bridgehead naphthalene featuring a highly twisted structure as confirmed by X-ray crystallography characterization. Such a twisted conformation works together with its phosphonium substituents to release the antiaromaticity in the planar conformation of the metal-bridgehead naphthalene. Our findings prove the bridgehead involvement of transition metals in unexpected aromaticity modifications and open an avenue for novel metal-bridgehead complexes.

SCI ; EI

英语

NI期刊

第一 ; 通讯

National Natural Science Foundation of China["U1705254","21873079","21931002"] ; Shenzhen Science and Technology Innovation Committee[JCYJ20200109140812302] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:000703999100012

AMER CHEMICAL SOC

20214010965428

Aromatization ; Conformations ; Mineral oils ; Organometallics ; Transition metals ; X ray crystallography

Petroleum Products:513.3 ; Metallurgy and Metallography:531 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Compounds:804.1 ; Crystal Lattice:933.1.1

2-s2.0-85116059493

Scopus

1.Shenzhen Grubbs Institute,Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China
2.State Key Laboratory of Physical Chemistry of Solid Surfaces,Collaborative Innovation Center of Chemistry for Energy Materials (IChEM),College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,361005,China
3.Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,361005,China

Tang，Chun,Zhao，Yu,Wu，Jingjing,et al. Releasing Antiaromaticity in Metal-Bridgehead Naphthalene[J]. Journal of the American Chemical Society,2021,143(38):15587-15592.

Tang，Chun.,Zhao，Yu.,Wu，Jingjing.,Chen，Zhixin.,Liu，Liu Leo.,...&Xia，Haiping.(2021).Releasing Antiaromaticity in Metal-Bridgehead Naphthalene.Journal of the American Chemical Society,143(38),15587-15592.

Tang，Chun,et al."Releasing Antiaromaticity in Metal-Bridgehead Naphthalene".Journal of the American Chemical Society 143.38(2021):15587-15592.