Rational, facile synthesis and characterization of the neutral mixed-metal organometallic oxides Cp*2MoxW6-xO 17 (Cp* = C5Me5, x = 0, 2, 4, 6)
No Thumbnail Available
Date
2009
Journal Title
Journal ISSN
Volume Title
Publisher
Abstract
The reaction of the bis(pentamethylcyclopentadienyl)pentaoxidodimetal complexes Cp*2M2O5 with four equivalents of Na2M′O4 (M, M′ = Mo, W) in acidic aqueous medium constitutes a soft and selective entry into neutral Lindqvist-type organometallic mixed-metal oxides Cp*2MoxW 6-xO17 [x = 6 (1), 4 (2), 2 (3), 0 (4)]. The identity of the complexes is demonstrated by elemental analyses, thermogravimetric analyses and infrared spectroscopy. Thermal degradation of 1-4 up to above 500 °C leads to Mox/6W1-;x/6O3. The molecular identity and geometry of compound 2 is further confirmed by a fit of the powder X-ray diffraction pattern with a model obtained from, previously reported, single-crystal X-ray structures of 1 and 4, with which 2 is isomorphous. DFT calculations on models obtained by replacing Cp* with Cp (I-IV) validate the structural assignments and assist in the assignment of the M,M′-O vibrations. © Wiley-VCH Verlag GmbH & Co. KGaA.