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Novel Ti−O−Ti Bonding Species Constructed in a Metal−Oxide Cluster:  Reaction Products of Bis(oxalato)oxotitanate(IV) with the Dimeric, 1,2-Dititanium(IV)-Substituted Keggin Polyoxotungstate

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journal contribution
posted on 2006-10-02, 00:00 authored by Kunihiko Hayashi, Hideyuki Murakami, Kenji Nomiya
The preparation and structural characterization of a novel Ti−O−Ti bonding complex constructed in a dilacunary α-Keggin polyoxometalate (POM), [[{Ti(ox)(H2O)}4(μ-O)3](α-PW10O37)]7- (H2ox = oxalic acid) (1a), are described. The water-soluble, crystalline complex with a formula of K6H[1a]·0.5KCl·10H2O (1p) was prepared as the bulk sample in 28.0% (0.51 g scale) yield in a 1:4 molar-ratio reaction of the dititanium(IV)-substituted, dimeric form of an α-Keggin POM, K10[(α-1,2-PW10Ti2O39)2]·18H2O, with the titanium(IV) source K2[TiO(ox)2]·2H2O in HCl-acidic solution (pH 0.08). Prior to formation of 1p, the KCl-free crystalline compound (1c) obtained was characterized with X-ray crystallography. The compound 1p was unequivocally characterized with complete elemental analysis, thermogravimetric and differential thermal analyses (TG/DTA), FTIR, and solution (31P, 183W, and 13C) NMR spectroscopy. The molecular structure of 1a was determined. The POM 1a in the solid state was composed of the four octahedral Ti groups (four guests), i.e., the two Ti−O−Ti groups linked with the μ-O atom, incorporated to the two adjacent, octahedral vacant sites (two hosts) in the dilacunary Keggin POM. The formation of 1a, as well as the recently found POM [{Ti(ox)(H2O)}2(μ-O)](α-PW11O39)]5- (2a), was strongly dependent on the reaction with [TiO(ox)2]2-, i.e., the anionic titanium(IV) complex as the titanium(IV) source. The POM 1a is contrasted to most titanium(IV)-substituted POMs consisting of a combination of a monolacunary site (one host) and an octahedral Ti group (one guest) and also contrasted to 2a as a combination of a monolacunary site (one host) and two octahedral Ti groups or a Ti−O−Ti group (two guests).