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

Open Access
Authors
  • G. Hierlmeier
  • P. Coburger
  • D.J. Scott
  • T.M. Maier
Publication date 25-10-2021
Journal Chemistry-A European Journal
Volume | Issue number 27 | 60
Pages (from-to) 14936-14946
Number of pages 11
Organisations
  • Faculty of Science (FNWI) - Van 't Hoff Institute for Molecular Sciences (HIMS)
Abstract
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 Möβbauer spectroscopies as well as quantum chemical calculations.
Document type Article
Note With supplementary file.
Language English
Related dataset CCDC 2101039: Experimental Crystal Structure Determination CCDC 2101040: Experimental Crystal Structure Determination CCDC 2101042: Experimental Crystal Structure Determination CCDC 2101043: Experimental Crystal Structure Determination CCDC 2101036: Experimental Crystal Structure Determination CCDC 2101037: Experimental Crystal Structure Determination CCDC 2101038: Experimental Crystal Structure Determination CCDC 2101041: Experimental Crystal Structure Determination CCDC 2101044: Experimental Crystal Structure Determination
Published at https://doi.org/10.1002/chem.202102335
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