Selective synthesis of triangular cluster oxido-sulfidocomplexes of Mo and W: High yield preparations of [Mo 3O 2S 2(H 2O) 9] 4+, [W 3O 2S 2(H 2O) 9] 4+, [W 2MoO 2S 2(H 2O) 9] 4+ and their derivatization

Abstract

Reaction of [Mo 2O 2(μ-S) 2(H 2O) 6] 2+ with Mo(CO) 6 or metallic Mo under hydrothermal conditions (140 °C, 4 M HCl) gives oxido-sulfido cluster aqua complex [Mo 3(μ 3-S)(μ-O) 2(μ-S)(H 2O) 9] 4+ ( 1). Similarly, [W 3(μ 3-S)(μ-O) 2(μ-S)(H 2O) 9] 4+ ( 2) is obtained from [W 2O 2(μ-S) 2(H 2O) 6] 2+ and W(CO) 6. While reaction of [Mo 2O 2(μ-S) 2(H 2O) 6] 2+ with W(CO) 6 mainly proceeds as simple reduction to give 1, [W 2O 2(μ-S) 2(H 2O) 6] 2+ with Mo(CO) 6 produces new mixed-metal cluster [W 2Mo(μ 3-S)(μ-O) 2(μ-S)(H 2O) 9] 4+ ( 3) as main product. From solutions of 1 in HCl supramolecular adduct with cucurbit[6]uril (CB[6]) {[Mo 3O 2S 2(H 2O) 6Cl 3] 2CB[6]}Cl 2⋅18H 2O ( 4) was isolated and structurally characterized. The aqua complexes were converted into acetylacetonates [M 3O 2S 2(acac) 3(py) 3]PF 6 (M 3 = Mo 3, W 3, W 2Mo; 5a– c), which were characterized by X-ray single crystal analysis, electrospray ionization mass spectrometry and 1H NMR spectroscopy. Crystal structure of (H 5O 2)(Me 4N) 4[W 3(μ 3-S)(μ 2-S)(μ 2-O) 2(NCS) 9] ( 6), obtained from 2, is also reported.