Rational synthesis and characterization of the mixed-metal organometallic polyoxometalates [Cp*Mo xW 6-xO 18] - (x = 0, 1, 5, 6)

Taban-Çşkan G.; Mesquita Fernandes D.; Daran J.-C.; Agustin D.; Demirhan F.; Poli R.

Rational synthesis and characterization of the mixed-metal organometallic polyoxometalates [Cp*Mo xW 6-xO 18] - (x = 0, 1, 5, 6)

Date

2012

Authors

Taban-Çşkan G.

Mesquita Fernandes D.

Abstract

The reaction between the oxometallic complexes Cp* 2M 2O 5 and Na 2M′O 4 (M, M′ = Mo, W) in a 1:10 molar ratio in an acidic aqueous medium constitutes a mild and selective entry into the anionic Lindqvist-type hexametallic organometallic mixed oxides [Cp*Mo xW 6-xO 18] - [x = 6 (1), 5 (2), 1 (3), 0 (4)]. All of these compounds have been isolated as salts of nBu 4N + (a), nBu 4P + (b), and Ph 4P + (c) cations and two of them (1 and 3) also with the n-butylpyridinium (nBuPyr +, d) cation. The compounds have been characterized by elemental analyses, thermogravimetric analyses, electrospray mass spectrometry, and IR spectroscopy. The molecular identity and geometry of compounds 1c, 2a, and 2c have been confirmed by single-crystal X-ray diffraction. Density functional theory calculations on models obtained by replacing Cp* with Cp (I-IV) have provided information on the assignment of the terminal M=O and bridging M-O-M vibrations. © 2012 American Chemical Society.