Di‐ tert ‐butyldiphosphatetrahedran: Katalytische Synthese des freien Phosphaalkin‐Dimers. Di‐tert‐butyldiphosphatetrahedrane: Catalytic Synthesis of the Elusive Phosphaalkyne Dimer

URN to cite this document:

urn:nbn:de:bvb:355-epub-457258 Copy

DOI to cite this document:

10.5283/epub.45725 Copy

Hierlmeier, Gabriele ; Coburger, Peter ; Bodensteiner, Michael ; Wolf, Robert

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Date of publication of this fulltext: 17 May 2021 11:56

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Details

Item type:	Article
Journal or Publication Title:	Angewandte Chemie International Edition
Publisher:	Wiley
Place of Publication:	WEINHEIM
Volume:	58
Number of Issue or Book Chapter:	47
Page Range:	pp. 16918-16922
Date:	2019
Institutions:	Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf
Identification Number:	Value Type 10.1002/anie.201910505 DOI
Related URLs:	URL URL Type UNSPECIFIED Publisher
Keywords:	TETRAHEDRANE; COMPOUND; CYCLOOLIGOMERIZATION; CRYSTAL; dimerization; homogeneous catalysis; nickel; phosphaalkynes; phosphorus
Dewey Decimal Classification:	500 Science > 540 Chemistry & allied sciences
Status:	Published
Refereed:	Yes, this version has been refereed
Created at the University of Regensburg:	Yes
Item ID:	45725

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Abstract

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 ...

Abstract

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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