Syntheses and X-ray crystal structures of novel oxonium ion-12-crown-4 complexes isolated from liquid clathrate media

Atwood, Jerry L., and Junk, Peter C. (2000) Syntheses and X-ray crystal structures of novel oxonium ion-12-crown-4 complexes isolated from liquid clathrate media. Journal of Coordination Chemistry, 51 (2). pp. 379-397.

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Abstract

The reactions of Mo(CO)₆ and W(CO)₆ with HCl(g) in the presence of 12-crown-4 and H₂O have been investigated in toluene. For both reactions, two products were isolated, depending on the oxidation of the metal center. For molybdenum, the Mo(III) species, [H₃O⁺·12-crown-4]₃[Mo₂Cl₉³⁻], 1, was obtained from the liquid clathrate layer in the reaction mixture. Upon air oxidation of the reaction mixture, the Mo(v) complex, [H₇O₃⁻·H₄O₂⁺·(12-crown-4)₂][MoOCl₄(H₂O)⁻]₂, 2, rapidly formed. For tungsten, the W(II) species, [(H₅O₂⁺)₂·12-crown-4][W(CO)₄Cl⁻₃]₂, 3, deposited from the liquid clathrate layer which upon oxidation formed the W(v) complex, [H₃O⁺·12-crown-4][WOCl₄(H₂O)⁻], 4. These reactions were promoted by UV radiation and formed liquid clathrates almost immediately upon reaction. X-ray crystal structures were performed on each compound. Complexes 1 and 4 have H₃O⁺ oxonium ions involved in complex hydrogen bonded arrays with the 12-crown-4 acceptor molecules. The H₅O₂⁺ oxonium ions in 2 and 3 contain extremely short O…O separations, equivalent to the shortest O-H…O bonds known. Also isolated in complex 2 was the H₇O₃⁺ oxonium ion which contains an unusual linear O…O…O core.

Item ID: 12909
Item Type: Article (Refereed Research - C1)
ISSN: 1029-0389
Date Deposited: 02 Nov 2012 00:28
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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