Bicyclo[1.1.0]tetragermane‐2,4‐diide Diradicaloid
Abstract
Abstract The synthesis, structure, and reactivity of the bicyclo[1.1.0]tetragermane‐2,4‐diide compound [(ADC)Ge 2 ] 2 ( 3 ), which features a Ge 4 core bridged by two anionic dicarbene frameworks (ADC = PhC{N(Dipp)C} 2 ; Dipp = 2,6‐iPr 2 C 6 H 3 ), are reported. Treatment of an alkyne‐functionalized amidine Me 3 SiC≡CN(Dipp)C(Ph)═N(Dipp) ( 1 ) with GeCl 4 affords [(ADC)GeCl 3 (GeCl 4 )] ( 2 ). KC 8 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 −1 . 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)] 2 ( 4 ). Treatment of 3 with Fe 2 (CO) 9 gives [(ADC)Ge(Ge{Fe(CO) 4 })] 2 ( 5 ) .
Article Details
Authors (6)
Falk Ebeler
Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry Universität Bielefeld Universitätsstrasse 25 D‐33615 Bielefeld Germany
Yury V. Vishnevskiy
Molecular Inorganic Chemistry and Catalysis Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universität Bielefeld Universitätsstrasse 25 D‐33615 Bielefeld Germany
Jan‐Hendrik Lamm
Lehrstuhl für Anorganische Chemie und Strukturchemie (ACS), Fakultät für Chemie Universität Bielefeld Universitätsstraße 25 D‐33615 Bielefeld Germany
Beate Neumann
Molecular Inorganic Chemistry and Catalysis Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universität Bielefeld Universitätsstrasse 25 D‐33615 Bielefeld Germany
Hans‐Georg Stammler
Molecular Inorganic Chemistry and Catalysis Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universität Bielefeld Universitätsstrasse 25 D‐33615 Bielefeld Germany
Rajendra S. Ghadwal
Molecular Inorganic Chemistry and Catalysis Inorganic and Structural Chemistry Center for Molecular Materials Faculty of Chemistry Universität Bielefeld Universitätsstrasse 25 D‐33615 Bielefeld Germany