具有双配位Ga(i)原子的环状碳环镓烯和双镓烯。
Annulated carbocyclic gallylene and bis-gallylene with two-coordinated Ga(i) atoms.
作者信息
Merschel Arne, Heda Shkelqim, Vishnevskiy Yury V, Neumann Beate, Stammler Hans-Georg, Ghadwal Rajendra S
机构信息
Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld Universitätsstrasse 25 D-33615 Bielefeld Germany
出版信息
Chem Sci. 2024 Nov 14;16(5):2222-2230. doi: 10.1039/d4sc06782g. eCollection 2025 Jan 29.
The first carbocyclic gallylene [(ADC)Ga(GaI)] and bis-gallylene [(ADC)Ga] (ADC = PhC{N(Dipp)C}; Dipp = 2,6-iPrCH) featuring a central CGa ring annulated between two 1,3-imidazole rings are prepared by KC reductions of [(ADC)GaI]. Treatment of [(ADC)Ga] with Fe(CO) affords complex [(ADC)GaFe(CO)] in which each Ga(i) atom serves as a two-electron donor. [(ADC)Ga] activates white phosphorus (P) and the C -F bond of aryl fluorides (ArF) to yield compounds [(ADC)Ga(P)] and -/-[(ADC)GaF(Ar)], respectively. [(ADC)Ga] undergoes oxidation with (MeS)AuCl to give [(ADC)GaCl], while with PhN[double bond, length as m-dash]NPh it forms [1 + 4]-cycloaddition product [(ADC)GaN(Ph)N[double bond, length as m-dash]CH] by the dearomatization of one of the phenyl rings.
首个含碳环的镓烯[(ADC)Ga(GaI)]和双镓烯[(ADC)Ga]（ADC = PhC{N(Dipp)C}；Dipp = 2,6 - iPr₂CH），其中心CGa环稠合在两个1,3 - 咪唑环之间，通过[(ADC)GaI]的KC还原反应制备得到。[(ADC)Ga]与Fe(CO)₅反应生成配合物[(ADC)GaFe(CO)₅]，其中每个Ga(i)原子作为双电子供体。[(ADC)Ga]可活化白磷(P)以及芳基氟化物(ArF)的C - F键，分别生成化合物[(ADC)Ga(P)]和[(ADC)GaF(Ar)]。[(ADC)Ga]与(MeS)AuCl发生氧化反应生成[(ADC)GaCl]，而与PhN=NPh反应时，通过其中一个苯环的去芳构化形成[1 + 4]环加成产物[(ADC)GaN(Ph)N=CH]。
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