Heptanuclear Fe 5 Cu 2 -Phenylgermsesquioxane containing 2,2′-Bipyridine: Synthesis, Structure, and Catalytic Activity in Oxidation of C–H Compounds

Alexey Bilyachenko (1) , Victor N. Khrustalev (1) , Yan Zubavichus , Lidia Shul’pina , Alena Kulakova (1) , Xavier Bantreil (2) , Frédéric Lamaty (2) , Mikhail Levitsky (1) , Evgeniy Gutsul , Elena V Shubina (1) , Georgiy Shul’pin

1 INEOS - A. N. Nesmeyanov Institute of Organoelement Compounds
2 IBMM - Institut des Biomolécules Max Mousseron [Pôle Chimie Balard]

A new representative of an unusual family of metallagermaniumsesquioxanes, namely the heterometallic cagelike phenylgermsesquioxane (PhGeO 2) 12 Cu 2 Fe 5 (O)OH-(PhGe) 2 O 5 (bipy) 2 (2), was synthesized and structurally characterized. Fe(III) ions of the complex are coordinated by oxa ligands: (i) cyclic (PhGeO 2) 12 and acyclic (Ph 2 Ge 2 O 5) germoxanolates and (ii) O 2− and (iii) HO − moieties. In turn, Cu(II) ions are coordinated by both oxa (germoxanolates) and aza ligands (2,2′-bipyridines). This "hetero-type" of ligation gives in sum an attractive pagoda-like molecular architecture of the complex 2. Product 2 showed a high catalytic activity in the oxidation of alkanes to the corresponding alkyl hydroperoxides (in yields up to 30%) and alcohols (in yields up to 100%) and in the oxidative formation of benzamides from alcohols (catalyst loading down to 0.4 mol % in Cu/Fe).

Domaines: Chimie

Alexey Bilyachenko, Victor N. Khrustalev, Yan Zubavichus, Lidia Shul’pina, Alena Kulakova, et al.. Heptanuclear Fe 5 Cu 2 -Phenylgermsesquioxane containing 2,2′-Bipyridine: Synthesis, Structure, and Catalytic Activity in Oxidation of C–H Compounds. Inorganic Chemistry, 2018, 57 (1), pp.528-534. ⟨10.1021/acs.inorgchem.7b02881⟩. ⟨hal-02370705⟩