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Synthese und mehrfache Folgereaktivität von anionischen cyclo ‐E 3 ‐Ligandkomplexen (E=P, As)

Martin Piesch, Stephan Reichl, Michael Seidl, Gábor Balázs,
Published: 7 May 2021
 by  Wiley
Angewandte Chemie , Volume 133, pp 15228-15236; doi:10.1002/ange.202103683

Abstract: A synthetic pathway for the synthesis of novel anionic sandwich complexes with a cyclo‐E 3 (E = P, As) ligand as an end deck was developed giving [Cp’’’Co( η 3 ‐E 3 )] ‐ (Cp’’’ = 1,2,4‐tri‐tert‐butyl‐cyclopentadienyl, E = P ([ 5 ]), As ([ 6 ])) in good yields suitable for further reactivity studies. In the reaction with the chlorophosphanes R 2 PCl (R = Ph, Cy, t Bu), neutral complexes with a disubstituted cyclo‐E 3 P (E = P, As) ligand in [Cp’’’Co( η 3 ‐E 3 PR 2 )] (E = P ( 7a ‐ c ), As ( 9a ‐ c )) were obtained. These compounds can be partially or completely converted into complexes with a cyclo‐E 3 (E = P, As) ligand with an exocyclic {PR 2 } unit in [Cp’’’Co( η 2 :η 1 ‐E 3 PR 2 )] (E = P ( 8a ‐ c ), As ( 10a ‐ c ). Additionally, the insertion of the chlorosilylene [LSiCl] (L = ( t BuN) 2 CPh) into the cyclo‐E 3 ligand of [ 5 ] and [ 6 ] was achieved and the novel heteroatomic complexes [Cp’’’Co( η 3 ‐E 3 SiL)] (E = P ( 11 ), As ( 12 )) could be isolated. The reaction pathway was elucidated by DFT calculations.
Keywords: cyclo / ligand / converted / giving / 10a / neutral

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