title: Reactions of Isocyanides with Metal Carbyne Complexes: Isolation and Characterization of Metallacyclopropenimine Intermediates.
abstract: η2-Iminoketenyl species have often been postulated as the intermediates in nucleophile-induced carbyne-isocyanide C-C coupling processes. However, such species are elusive. Here we report direct formation of η2-iminoketenyl complexes from reactions of metallapentalyne with isocyanides. Our studies show that steric effects of N-substituents of the isocyanides play an important role in the stability of the three-membered metallacycles of the η2-iminoketenyl complexes. Sterically bulky isocyanides, such as tert-butyl or 1-adamantyl isocyanides, inhibit bending at the isocyanide nitrogen atoms, a requirement for formation of η2-iminoketenyl structures. Reactions of metallapentalyne with excess isocyanide allow the metal-bridged metallaindene derivativesto be isolated as a result of the isocyanide insertion into the M-Cασ bond of metallapentalyne.
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Ming
authors.initials: M
authors.lastname: Luo
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Lipeng
authors.initials: L
authors.lastname: Long
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Hong
authors.identifier: 0000-0003-3010-0806
authors.initials: H
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Yuhui
authors.initials: Y
authors.lastname: Yang
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Yuhui
authors.initials: Y
authors.lastname: Hua
authors.affiliation: State Key Laboratory of Molecular Vaccinology and Molecular Diagnostics and Center for Molecular Imaging and Translational Medicine, School of Public Health, Xiamen University , Xiamen 361102, China.
authors.forename: Gang
authors.identifier: 0000-0003-1466-6295
authors.initials: G
authors.lastname: Liu
authors.affiliation: Department of Chemistry, The Hong Kong University of Science and Technology , Clear Water Bay, Kowloon, Hong Kong.
authors.forename: Zhenyang
authors.identifier: 0000-0003-4104-8767
authors.initials: Z
authors.lastname: Lin
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Haiping
authors.initials: H
authors.lastname: Xia