| Abstrakt: |
While tetrahedranes as a family are scarce, neutral heteroatomic species are all but unknown, with the only reported example being AsP3. Herein, we describe the isolation of a neutral heteroatomic X2Y2 molecular tetrahedron (X, Y=p‐block elements), which also is the long‐sought‐after free phosphaalkyne dimer. Di‐tert‐butyldiphosphatetrahedrane, (tBuCP)2, is formed from the monomer tBuCP in a nickel‐catalyzed dimerization reaction using [(NHC)Ni(CO)3] (NHC=1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene (IMes) and 1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene (IPr)). Single‐crystal X‐ray structure determination of a silver(I) complex confirms the structure of (tBuCP)2. The influence of the N‐heterocyclic carbene ligand on the catalytic reaction was investigated, and a mechanism was elucidated using a combination of synthetic and kinetic studies and quantum chemical calculations. [ABSTRACT FROM AUTHOR] |
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