具有双配位 Ga(I) 原子的环状烯丙基镓和双烯丙基镓

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2024-11-14 DOI:10.1039/d4sc06782g

Rajendra S. Ghadwal, Arne Merschel, Shkelqim Heda, Yury V Vishnevskiy, Beate Neumann, Georg Stammler

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引用次数: 0

摘要

通过 KC8 还原 [(ADC)GaI2]2，制备出首个碳环烯丙基[(ADC)2Ga(GaI2)]和双烯丙基[(ADC)Ga]2（ADC = PhC{N(Dipp)C}2; Dipp = 2,6-iPr2C6H3），其特点是在两个 1,3-imidazole 环之间有一个 C4Ga2 中心环。用 Fe2(CO)9 处理[(ADC)Ga]2，得到复合物[(ADC)GaFe(CO)4]2，其中每个 Ga(I)原子都是双电子供体。[(ADC)Ga]2激活白磷（P4）和芳基氟化物（ArF）的Csp2-F键，分别生成化合物[(ADC)Ga(P4)]2和顺式/反式-[ADC)GaF(Ar)]2。[(ADC)Ga]2与(Me2S)AuCl发生氧化反应，生成[(ADC)GaCl2]2，而与PhN=NPh发生氧化反应，通过其中一个苯基环的脱芳烃作用，形成[1+4]-环加成产物[(ADC)GaN(Ph)N=C6H5]2。

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Annulated Carbocyclic Gallylene and Bis-Gallylene with Two-Coordinated Ga(I) Atoms

The first carbocyclic gallylene [(ADC)2Ga(GaI2)] and bis-gallylene [(ADC)Ga]2 (ADC = PhC{N(Dipp)C}2; Dipp = 2,6-iPr2C6H3) featuring a central C4Ga2 ring annulated between two 1,3-imidazole rings are prepared by KC8 reductions of [(ADC)GaI2]2. Treatment of [(ADC)Ga]2 with Fe2(CO)9 affords complex [(ADC)GaFe(CO)4]2 in which each Ga(I) atom serves as a two-electron donor. [(ADC)Ga]2 activates white phosphorus (P4) and the Csp2–F bond of aryl fluorides (ArF) to yield compounds [(ADC)Ga(P4)]2 and cis-/trans-[ADC)GaF(Ar)]2, respectively. [(ADC)Ga]2 undergoes oxidation with (Me2S)AuCl to give [(ADC)GaCl2]2, while with PhN=NPh it forms [1+4]-cycloaddition product [(ADC)GaN(Ph)N=C6H5]2 by the dearomatization of one of the phenyl rings.

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来源期刊

Chemical Science CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

4.80%

发文量

1352

审稿时长

2.1 months

期刊介绍： Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.