双环[1.1.0]四锗烷-2,4-二亚基双自由基体
Bicyclo[1.1.0]tetragermane-2,4-diide Diradicaloid.
作者信息
Ebeler Falk, Vishnevskiy Yury V, Lamm Jan-Hendrik, 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
Angew Chem Int Ed Engl. 2025 Sep 15;64(38):e202513772. doi: 10.1002/anie.202513772. Epub 2025 Aug 7.
The synthesis, structure, and reactivity of the bicyclo[1.1.0]tetragermane-2,4-diide compound [(ADC)Ge] (3), which features a Ge core bridged by two anionic dicarbene frameworks (ADC = PhC{N(Dipp)C}; Dipp = 2,6-iPrCH), are reported. Treatment of an alkyne-functionalized amidine MeSiC≡CN(Dipp)C(Ph)═N(Dipp) (1) with GeCl affords [(ADC)GeCl(GeCl)] (2). KC reduction of 2 yields 3 as a Venetian red crystalline solid. DFT calculations reveal a singlet ground state for 3 with the singlet-triplet energy gap of 14 kcal mol. CASSCF (complete active space self-consistent field) calculations suggest a modest diradical character (β = 9%) for 3. Compound 3 readily reacts with TEMPO (2,2,6,6-tetramethylpiperidinyloxyl) to yield the Ge─Ge bond-cleaved product, [(ADC)Ge(Ge-TEMPO)] (4). Treatment of 3 with Fe(CO) gives [(ADC)Ge(Ge{Fe(CO)})] (5).
报道了双环[1.1.0]四锗烷-2,4-二亚胺化合物[(ADC)Ge] (3)的合成、结构及反应活性，该化合物具有由两个阴离子型二卡宾骨架(ADC = PhC{N(Dipp)C}; Dipp = 2,6-iPr₂C₆H₃)桥连的Ge核。用GeCl₂处理炔基官能化脒MeSiC≡CN(Dipp)C(Ph)═N(Dipp) (1)得到[(ADC)GeCl(GeCl)] (2)。用KC对2进行还原得到呈威尼斯红晶体状的3。密度泛函理论计算表明3的基态为单重态，单重态-三重态能隙为14 kcal/mol。完全活性空间自洽场(CASSCF)计算表明3具有适度的双自由基特征(β = 9%)。化合物3很容易与2,2,6,6-四甲基哌啶氮氧化物(TEMPO)反应生成Ge─Ge键断裂产物[(ADC)Ge(Ge-TEMPO)] (4)。用Fe(CO)₅处理3得到[(ADC)Ge(Ge{Fe(CO)₅})] (5)。
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