Acyclic Germylones: Congeners of Allenes with a Central Germanium Atom

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	Acyclic Germylones: Congeners of Allenes with a Central Germanium Atom
	Li, Yan ; Mondal, Kartik Chandra ; Roesky, Herbert W. ; Zhu, Hongping ; Stollberg, Peter ; Herbst-Irmer, Regine ; Stalke, Dietmar ; Andrada, Diego M. ; Li Y(李彦) ; Zhu HP(朱红平)
刊名	http://dx.doi.org/10.1021/ja406112u
	2013
关键词	DIVALENT CARBON(0) COMPOUNDS PLANAR NICKEL-COMPLEXES THEORETICAL EVIDENCE DIRADICAL CHARACTER CORRELATION-ENERGY AB-INITIO DENSITY SILICON(0) CARBODICARBENES APPROXIMATION
英文摘要	Deutsche Forschungsgemeinschaft [RO 224/60-1]; Danish National Research Foundation [DNRF93]; Chinese Scholarship Council; The cyclic alkyl(amino) carbene (cAAC:)-stabilized acyclic germylones (Me-2-cAAC:)(2)Ge (1) and (Cy-2-cAAC:)(2)Ge (2) were prepared utilizing a one-pot synthesis of GeCl2(dioxane), cAAC:, and KC8 in a 1:2:2.1 molar ratio. Dark green crystals of compounds 1 and 2 were produced in 75 and 70% yields, respectively. The reported methods for the preparation of the corresponding silicon compounds turned out to be not applicable in the case of germanium. The single-crystal X-ray structures of 1 and 2 feature the C-Ge-C bent backbone, which possesses a three-center two-electron pi-bond system. Compounds 1 and 2 are the first acyclic germylones containing each one germanium atom and two cAAC: molecules. EPR measurements on compounds 1 and 2 confirmed the singlet spin ground state. DFT calculations on 1/2 revealed that the singlet ground state is more stable by similar to 16 to 18 kcal mol(-1) than that of the triplet state. First and second proton affinity values were theoretically calculated to be of 265.8 (1)/267.1 (2) and 180.4 (1)/183.8 (2) kcal mol(-1), respectively. Further calculations, which were performed at different levels suggest a singlet diradicaloid character of 1 and 2. The TD-DFT calculations exhibit an absorption band at similar to 655 nm in n-hexane solution that originates from the diradicaloid character of germylones 1 and 2.
语种	英语
出版者	AMER CHEMICAL SOC
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/88936]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Li, Yan,Mondal, Kartik Chandra,Roesky, Herbert W.,et al. Acyclic Germylones: Congeners of Allenes with a Central Germanium Atom[J]. http://dx.doi.org/10.1021/ja406112u,2013.
APA	Li, Yan.,Mondal, Kartik Chandra.,Roesky, Herbert W..,Zhu, Hongping.,Stollberg, Peter.,...&朱红平.(2013).Acyclic Germylones: Congeners of Allenes with a Central Germanium Atom.http://dx.doi.org/10.1021/ja406112u.
MLA	Li, Yan,et al."Acyclic Germylones: Congeners of Allenes with a Central Germanium Atom".http://dx.doi.org/10.1021/ja406112u (2013).