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Issue 22, 2010
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A systematic study on the activation of simple polyethers by MoCl5 and WCl6

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MoCl5, 1a, and WCl6, 1b, activate 1,3-dioxolane at room temperature in chlorinated solvents: the compound [MoOCl3{O[double bond, length as m-dash]C(H)OCH2CH2Cl}]2, 2, has been isolated from MoCl5/dioxolane. The mixed oxo-chloro species WOCl4, 1c, reacts with 1,3-dioxolane, selectively giving the coordination adduct WOCl41-C3H6O2), 3. Dimethoxymethane, CH2(OMe)2, undergoes activation including C–H bond cleavage when reacted with 1a to give the molybdenum complexes [MoOCl3{O[double bond, length as m-dash]C(H)OMe}]2, 4, and Mo2Cl5(OMe)5, 5. The reactions of 1b with CH2(OR)2 (R = Me, Et) proceed via O-abstraction with formation of the oxo-derivatives WOCl4[O(R)CH2Cl] (R = Me, 6a; R = Et, 6b) in admixture with equimolar amounts of RCl. The reactions of 1a,b with CMe2(OMe)2 lead to mesityl oxide, MeC(O)CH[double bond, length as m-dash]C(Me)2. A series of simple diethers of general formula ROCH2(CHR′)OR′′ are activated by 1a,b in CDCl3, usually via cleavage of C–O bonds at high temperature. The complex WCl5(OCH2CH2OMe), 7, has been detected in solution as an intermediate species in the course of the degradation of 1,2-dimethoxyethane (dme) by 1b. The activation of CH(OMe)3 by 1 is limited to C–O bonds and selectively gives methyl chloride and methylformate, which has been found coordinated in WOCl4[O[double bond, length as m-dash]C(H)OMe], 8. The organic fragments produced in the reactions have been detected by GC-MS and NMR analyses, upon hydrolysis of the reaction mixtures. Compounds 2 and 5, which have had their molecular structures ascertained by X-ray diffraction, represent rare examples of crystallographically-characterized dinuclear Mo(V) species containing both halides and oxygen ligands.

Graphical abstract: A systematic study on the activation of simple polyethers by MoCl5 and WCl6

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The article was received on 22 Jan 2010, accepted on 13 Apr 2010 and first published on 07 May 2010

Article type: Paper
DOI: 10.1039/C001377C
Dalton Trans., 2010,39, 5367-5376

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    A systematic study on the activation of simple polyethers by MoCl5 and WCl6

    S. Dolci, F. Marchetti, G. Pampaloni and S. Zacchini, Dalton Trans., 2010, 39, 5367
    DOI: 10.1039/C001377C

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