Premium
Di‐ tert ‐butyldiphosphatetrahedrane: Catalytic Synthesis of the Elusive Phosphaalkyne Dimer
Author(s) -
Hierlmeier Gabriele,
Coburger Peter,
Bodensteiner Michael,
Wolf Robert
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201910505
Subject(s) - carbene , chemistry , dimer , catalysis , imes , ligand (biochemistry) , monomer , single crystal , crystal structure , stereochemistry , medicinal chemistry , crystallography , organic chemistry , polymer , biochemistry , receptor
While tetrahedranes as a family are scarce, neutral heteroatomic species are all but unknown, with the only reported example being AsP 3 . Herein, we describe the isolation of a neutral heteroatomic X 2 Y 2 molecular tetrahedron (X, Y=p‐block elements), which also is the long‐sought‐after free phosphaalkyne dimer. Di‐ tert ‐butyldiphosphatetrahedrane, ( t BuCP) 2 , is formed from the monomer t BuCP 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 ( t BuCP) 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.