Hierlmeier, Gabriele and Coburger, Peter and Bodensteiner, Michael and Wolf, Robert (2019) Di-tert-butyldiphosphatetrahedrane: Catalytic Synthesis of the Elusive Phosphaalkyne Dimer. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 58 (47). pp. 16918-16922. ISSN 1433-7851, 1521-3773
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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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | TETRAHEDRANE; COMPOUND; CYCLOOLIGOMERIZATION; CRYSTAL; dimerization; homogeneous catalysis; nickel; phosphaalkynes; phosphorus |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 25 Mar 2020 08:36 |
| Last Modified: | 25 Mar 2020 08:36 |
| URI: | https://pred.uni-regensburg.de/id/eprint/25976 |
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