Direct P-functionalization of azobenzene by a cationic phosphidozirconocene complex

Adrien T. Normand (1, 2) , Constantin G. Daniliuc (2) , Gerald Kehr (2) , Pierre Le Gendre (1) , Gerhard Erker (2)

1 ICMUB - Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon]
2 Organisch-Chemisches Institut Munster

We report that the cationic phosphidozirconocene complex [(eta(5)-C5H5)(2)Zr(PCy2)][CH3B(C6F5)(3)] (II) reacts with azobenzene, resulting in the expedient formation of Zr complex (2) bound to a tridentate PNN ligand. This reaction proceeds by a mechanism of cooperative nucleophilic substitution of hydrogen. The intermediate sigma(H) adduct (1) has been characterized by NMR spectroscopy.

Mots clés: aromatic azo-compounds; alpha-oxocarboxylic acids; c-h functionalization; nucleophilic-substitution; cinnolinium salts; ortho-acylation; azoarenes; alcohols; hydrogen; azoxybenzenes

Domaines: Chimie; Chimie; Chimie inorganique

Adrien T. Normand, Constantin G. Daniliuc, Gerald Kehr, Pierre Le Gendre, Gerhard Erker. Direct P-functionalization of azobenzene by a cationic phosphidozirconocene complex. Dalton Transactions, 2016, 45 (9), pp.3711 - 3714. ⟨10.1039/c6dt00416d⟩. ⟨hal-01402859⟩