Synthesis and Structural Elucidation of Triazolylmolybdenum(VI) Oxide Hybrids and Their Behavior as Oxidation Catalysts

authors	Lysenko, AB; Senchyk, GA; Domasevitch, KV; Hauser, J; Fuhrmann, D; Kobalz, M; Krautscheid, H; Neves, P; Valente, AA; Goncalves, IS
nationality	International
journal	INORGANIC CHEMISTRY
keywords	OLEFIN EPOXIDATION; HYDROTHERMAL SYNTHESIS; CRYSTAL-STRUCTURE; CYCLOOCTENE EPOXIDATION; OPEN-FRAMEWORKS; BENZYL ALCOHOL; COORDINATION POLYMERS; SELECTIVE EPOXIDATION; MOLYBDENUM COMPLEXES; ALKENE EPOXIDATION
abstract	A large family of bifunctional 1,2,4-triazole molecular tectons (tr) has been explored for engineering molybdenum(VI) oxide hybrid solids. Specifically, tr ligands bearing auxiliary basic or acidic groups were of the type amine, pyrazole, 1H-tetrazole, and 1,2,4-triazole. The organically templated molybdenum(VI) oxide solids with the general compositions [MoO3(tr)], [Mo2O6(tr)], and [Mo2O6(tr)(H2O)(2)] were prepared under mild hydrothermal conditions or by refluxing in water. Their crystal structures consist of zigzag chains, ribbons, or helixes of alternating cis-{MoO4N2} or {MoO5N} polyhedra stapled by short [N-N]-tr bridges that for bitriazole ligands convert the motifs into 2D or 3D frameworks. The high thermal (235-350 degrees C) and chemical stability observed for the materials makes them promising for catalytic applications. The molybdenum(VI) oxide hybrids were successfully explored as versatile oxidation catalysts with tert-butyl hydroperoxide (TBHP) or aqueous H2O2 as an oxygen source, at 70 degrees C. Catalytic performances were influenced by the different acidic basic properties and steric hindrances of coordinating organic ligands as well as the structural dimensionality of the hybrid.
publisher	AMER CHEMICAL SOC
issn	0020-1669
year published	2015
volume	54
issue	17
beginning page	8327
ending page	8338
digital object identifier (doi)	10.1021/acs.inorgchem.5b01007
web of science category	Chemistry, Inorganic & Nuclear
subject category	Chemistry
unique article identifier	WOS:000361085800022