Phosphine-Stabilized Germylidenylpnictinidenes as Synthetic
Equivalents of Heavier Nitrile and Isocyanide in Cycloaddition Reactions with Alkynes
Yuhao He1#, Chenshu Dai2#, Dongmin Wang1, Jun Zhu2,*（朱军）, and Gengwen Tan1,*（谭庚文）
1 College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
2 State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
# Y.H. and C.D. contributed equally
J. Am. Chem. Soc. 2022, 144, 5126--5135
The reactions of chlorogermylene Ms FluindtBu-GeCl 1, supported by a sterically encumbered hydrindacene ligand Ms FluindtBu, withNaPCO(dioxane)2.5 and NaAsCO(18-c-6) in the presence of trimethylphosphine afffforded trimethylphosphinestabilized germylidenyl-phosphinidene 2 and -arsinidene 3, respectively. Structural and computational investigations reveal that the Ge−E′ bond (E′ = P and As) features a multiple-bond character. 2 and 3 exhibit diverse reactivity toward trimethylsilylacetylene and 4-tetrabutylphenylacetylene. Specififically, 2 underwent cycloadditions with both alkynes affffording the fifirst sixmembered aromatic phosphagermabenzen-1-ylidenes 4 and 5, respectively, through the heavier isocyanide intermediate Ms FluindtBu-PGe. In contrast, 3 could serve as a synthetic equivalent of heavier isocyanides and nitriles when treated with trimethylsilylacetylene and 4-tetrabutylphenylacetylene yielding arsagermene 6 and arsolylgermylene 7, respectively. The reaction mechanisms for the cycloadditions were investigated through density functional theory calculations. The reactivity studies highlight the potential of 2 and 3 in accessing heavy main-group element-containing heterocycles.
链接： //pubs.acs.org/doi/10.1021/jacs.2c00305
