Abstract
Phosphine‐stabilized germaborenes featuring an unprecedented Ge=B double bond with short B⋅⋅⋅Ge contacts of 1.886(2) (4) and 1.895(3) Å (5) were synthesized starting from an intramolecular germylene–phosphine Lewis pair (1). After oxidative addition of boron trihalides BX3 (X=Cl, Br), the addition products were reduced with magnesium and catalytic amounts of anthracene to give the borylene derivatives in yields of 78 % (4) and 57 % (5). These halide‐substituted germaborenes were characterized by single‐crystal structure analysis, and the electronic structures were studied by quantum‐chemical calculations. According to an NBO NRT analysis, the dominating Lewis structure contains a Ge=B double bond. The germaborenes undergo a reversible, photochemically initiated [2+2] cycloaddition with the phenyl moiety of a terphenyl substituent at room temperature, forming a complex heterocyclic structure with GeIV in a strongly distorted coordination environment.
Highlights
Phosphine-stabilized germaborenes featuring an unprecedented Ge=B double bond with short B···Ge contacts of 1.886(2) (4) and 1.895(3) (5) were synthesized starting from an intramolecular germylene–phosphine Lewis pair (1)
After oxidative addition of boron trihalides BX3 (X = Cl, Br), the addition products were reduced with magnesium and catalytic amounts of anthracene to give the borylene derivatives in yields of 78 % (4) and 57 % (5)
These halide-substituted germaborenes were characterized by single-crystal structure analysis, and the electronic structures were studied by quantum-chemical calculations
Summary
Phosphine-stabilized germaborenes featuring an unprecedented Ge=B double bond with short B···Ge contacts of 1.886(2) (4) and 1.895(3) (5) were synthesized starting from an intramolecular germylene–phosphine Lewis pair (1). We report on the synthesis of phosphine-stabilized germaborenes.[1ag] The intramolecular Lewis pair 1 was reacted with boron trihalides, and the oxidative addition products 2 and 3 were isolated in high yield and characterized (Scheme 2).
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