Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 47, Pages 16918-16922Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201910505
Keywords
dimerization; homogeneous catalysis; nickel; phosphaalkynes; phosphorus
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Funding
- European Research Council [CoG 772299]
- Fonds der Chemischen Industrie
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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.
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