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Annulated Carbocyclic Gallylene and Bis-Gallylene with Two-Coordinated Ga(I) Atoms
Chemical Science ( IF 7.6 ) Pub Date : 2024-11-14 , DOI: 10.1039/d4sc06782g
Rajendra S. Ghadwal, Arne Merschel, Shkelqim Heda, Yury V Vishnevskiy, Beate Neumann, Georg Stammler

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.

中文翻译:


具有两个配位 Ga(I) 原子的环状碳环没食子烯和双没食子烯



第一碳环没食子烯 [(ADC)2Ga(GaI2)] 和双没食子烯 [(ADC)Ga]2 (ADC = PhC{N(Dipp)C}2;Dipp = 2,6-iPr2C6H3)具有一个中心C4Ga2环,该环在两个1,3-咪唑环之间,通过[(ADC)GaI2] 2的KC8还原制备。用 Fe2(CO)9 处理 [(ADC)Ga]2 得到络合物 [(ADC)GaFe(CO)4]2,其中每个 Ga(I) 原子都充当两个电子供体。[(ADC)Ga]2 激活白磷 (P4) 和芳基氟化物 (ArF) 的 Csp2–F 键,分别产生化合物 [(ADC)Ga(P4)]2 和顺式/反式 [ADC)GaF(Ar)]2。[(ADC)Ga]2 与 (Me2S)AuCl 发生氧化,得到 [(ADC)GaCl2]2,而与 PhN=NPh 一起,它通过其中一个苯环的脱芳烃形成 [(ADC)GaN(Ph)N=C6H5]2 的环加成产物 [(ADC)GaN(Ph)N=C6H5]2。
更新日期:2024-11-14
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