Di‐tert‐butyldiphosphatetrahedrane as a Source of 1,2‐Diphosphacyclobutadiene Ligands

Reactions of di‐tert‐butyldiphosphatetrahedrane (1) with cycloocta‐1,5‐diene‐ or anthracene‐stabilised metalate anions of iron and cobalt consistently afford complexes of the rarely encountered 1,2‐diphosphacyclobutadiene ligand, which have previously been very challenging synthetic targets. The sub...

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Bibliographic Details
Published in:Chemistry : a European journal 2021-10, Vol.27 (60), p.14936-14946
Main Authors: Hierlmeier, Gabriele, Coburger, Peter, Scott, Daniel J., Maier, Thomas M., Pelties, Stefan, Wolf, Robert, Pividori, Daniel M., Meyer, Karsten, Leest, Nicolaas P., Bruin, Bas
Format: Article
Language:English
Subjects:
Anions
Anthracene
Chemistry
Cobalt
iron
Isomers
Ligands
NMR
Nuclear magnetic resonance
phosphaalkyne oligomers
phosphatetrahedranes
phosphorus
Quantum chemistry
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Summary:Reactions of di‐tert‐butyldiphosphatetrahedrane (1) with cycloocta‐1,5‐diene‐ or anthracene‐stabilised metalate anions of iron and cobalt consistently afford complexes of the rarely encountered 1,2‐diphosphacyclobutadiene ligand, which have previously been very challenging synthetic targets. The subsequent reactivity of 1,2‐diphosphacyclobutadiene cobaltates toward various electrophiles has also been investigated and is compared to reactions of related 1,3‐diphosphacyclobutadiene complexes. The results highlight the distinct reactivity of such isomeric species, showing that the 1,2‐isomers can act as precursors for previously unknown triphospholium ligands. The electronic structures of the new complexes were investigated by several methods, including NMR, EPR and Mößbauer spectroscopies as well as quantum chemical calculations. Reactions of iron and cobalt metalates with di‐tert‐butyldiphosphatetrahedrane readily afford 1,2‐diphosphacyclobutadiene complexes. The corresponding 1,3‐isomers were accessed by dimerisation of tert‐butylphosphaalkyne on the metal centre. The reactivity of 1,2‐ and 1,3‐diphosphacyclobutadiene cobaltates toward electrophiles was studied and the electronic structures of the new metalates were investigated by spectroscopy and quantum chemical calculations.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202102335