Heptanuclear Fe5Cu2-Phenylgermsesquioxane containing 2,2'-Bipyridine: Synthesis, Structure, and Catalytic Activity in Oxidation of C-H Compounds

Alexey N Bilyachenko; Victor N Khrustalev; Yan V Zubavichus; Lidia S Shul'pina; Alena N Kulakova; Xavier Bantreil; Frédéric Lamaty; Mikhail M Levitsky; Evgeniy I Gutsul; Elena S Shubina; Georgiy B Shul'pin

doi:10.1021/acs.inorgchem.7b02881

Heptanuclear Fe₅Cu₂-Phenylgermsesquioxane containing 2,2'-Bipyridine: Synthesis, Structure, and Catalytic Activity in Oxidation of C-H Compounds

Inorg Chem. 2018 Jan 2;57(1):528-534. doi: 10.1021/acs.inorgchem.7b02881. Epub 2017 Dec 12.

Authors

Affiliations

¹ Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences , Vavilov Str., 28, 119991 Moscow, Russia.
² Peoples' Friendship University of Russia (RUDN University) , Miklukho-Maklay Str., 6, 117198 Moscow, Russia.
³ National Research Center "Kurchatov Institute" , Akademika Kurchatova pl., 1, 123182 Moscow, Russia.
⁴ Institut des Biomolécules Max Mousseron (IBMM), UMR 5247, CNRS, Université de Montpellier ENSCM, Site Triolet , Place Eugène Bataillon, 34095 Montpellier cedex 5, France.
⁵ Semenov Institute of Chemical Physics, Russian Academy of Sciences , ulitsa Kosygina, dom 4, Moscow 119991, Russia.
⁶ Plekhanov Russian University of Economics , Stremyannyi pereulok, dom 36, Moscow 117997, Russia.

PMID: 29232118
DOI: 10.1021/acs.inorgchem.7b02881

Abstract

A new representative of an unusual family of metallagermaniumsesquioxanes, namely the heterometallic cagelike phenylgermsesquioxane (PhGeO₂)₁₂Cu₂Fe₅(O)OH(PhGe)₂O₅(bipy)₂ (2), was synthesized and structurally characterized. Fe(III) ions of the complex are coordinated by oxa ligands: (i) cyclic (PhGeO₂)₁₂ and acyclic (Ph₂Ge₂O₅) 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).