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

Hierlmeier, Gabriele; Coburger, Peter; Scott, Daniel J.; Maier, Thomas M.; Pelties, Stefan; Wolf, Robert; Pividori, Daniel M.; Meyer, Karsten; van Leest, Nicolaas P.; de Bruin, Bas

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.

QUANTUM wells; ELECTRON paramagnetic resonance spectroscopy; ELECTRONIC structure; COBALT; IRON; ELECTROPHILES

Chemistry - A European Journal, 2021, Vol 27, Issue 60, p14936

0947-6539

Academic Journal

10.1002/chem.202102335