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Element–Element Bond Formation upon Oxidation and Reduction
Author(s) -
Piesch Martin,
Graßl Christian,
Scheer Manfred
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201916622
Subject(s) - chemistry , ligand (biochemistry) , cyclopentadienyl complex , allylic rearrangement , redox , medicinal chemistry , stereochemistry , potassium , crystallography , bond length , crystal structure , inorganic chemistry , catalysis , organic chemistry , biochemistry , receptor
The redox chemistry of [(Cp′′′Co) 2 (μ,η 2 :η 2 ‐E 2 ) 2 ] (E=P ( 1 ), As ( 2 ); Cp′′′=1,2,4‐tri( tert ‐butyl)cyclopentadienyl) was investigated. Both compounds can be oxidized and reduced twice. That way, the monocations [(Cp′′′Co) 2 (μ,η 4 :η 4 ‐E 4 )][X] (E=P, X=BF 4 ( 3 a ), [FAl] ( 3 b ); E=As, X=BF 4 ( 4 a ), [FAl] ( 4 b )), the dications [(Cp′′′Co) 2 (μ,η 4 :η 4 ‐E 4 )][TEF] 2 (E=P ( 5 ), As ( 6 )), and the monoanions [K(18‐c‐6)(dme) 2 ][(Cp′′′Co) 2 (μ,η 4 :η 4 ‐E 4 )] (E=P ( 7 ), As ( 8 )) were isolated. Further reduction of 7 leads to the dianionic complex [K(18‐c‐6)(dme) 2 ][K(18‐c‐6)][(Cp′′′Co) 2 (μ,η 3 :η 3 ‐P 4 )] ( 9 ), in which the cyclo‐P 4 ligand has rearranged to a chain‐like P 4 ligand. Further reduction of 8 can be achieved with an excess of potassium under the formation of [K(dme) 4 ][(Cp′′′Co) 2 (μ,η 3 :η 3 ‐As 3 )] ( 10 ) and the elimination of an As 1 unit. Compound 10 represents the first example of an allylic As 3 ligand incorporated into a triple‐decker complex.