Base promoted successive dealkylation steps of molybdenum alkoxides leading to a row of novel 1D and 2D polymeric frameworks of potassium–molybdenum oxomethoxides. (8th January 2015)

• Record Type: Journal Article
• Authors: Kuznetsov, Denis A.; Kovaleva, Nadezhda V.; Fedyanin, Ivan V.; Lyssenko, Konstantin A.; Bazhenova, Tamara A.
• Is Part Of: Polyhedron. Volume 85(2015)
• Page Start: 809
• Page End: 813
• Publication Date: 2015-01-08
• Subjects: Molybdenum -- Heterometallic alkoxides -- Dealkylation -- Carbonate -- Precursor; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2014.10.009
• Languages: English
• ISSNs: 0277-5387

Abstract

Abstract : Graphical abstract: A series of heterometallic potassium–molybdenum oxo-alkoxides with various K/Mo stoichiometries, arranged into different supramolecular frameworks, was synthesized by the reaction of MoCl5 methanolysis in the presence of KOCH3 . An unusual example of the reaction of non-hydrolytic oxo-group formation affording a mixed-bridged oxo-alkoxo compound is presented. Abstract: The MoCl5 methanolysis reaction, in the presence of basic agents providing weakly alkaline media, leads to the formation of a Mo–Mo triply bridged anionic dimeric complex with a solvated potassium counter-ion, [K(CH3 OH)2 Mo2 O2 (μ2 -OCH3 )3 (OCH3 )4 ] (1 ), that represents the first structurally characterized Mo–K oxoalkoxide . Here we describe its further reactivity, i.e. the MoCl5 methanolysis reaction in the presence of an additional equivalent of base which leads to demethylation of the one of μ2 -bridging alkoxides, thus giving an unusual oxo-, dimethoxo-bridged cluster, [K2 (CH3 OH)Mo2 O2 (μ2 -OCH3 )2 (μ2 -O)(OCH3 )4 ] (2 ). Subsequent transformation with the generation of the formally {Mo–Mo} 4− species in [K4 (CH3 OH)6 Mo2 O2 (μ2 -O)2 (OCH3 )2 (CO3 )2 ] (3 ) was achieved via addition of an extra amount of base in the presence of potassium carbonate along with providing more vigorous reaction conditions.