Practical Synthetic Routes to Solvates of U(OTf)3: X-ray Crystal Structure of [U(OTf)3(MeCN)3]n, a Unique U(III) Coordination Polymer
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- 作者：Louise Natrajan ; Marinella Mazzanti ; Jean-Philippe Bezombes ; and Jacques Pé ; caut
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：August 22, 2005
- 年：2005
- 卷：44
- 期：17
- 页码：6115 - 6121
- 全文大小：150K
- 年卷期：v.44,no.17(August 22, 2005)
- ISSN：1520-510X
文摘
The reaction of UH3 or U metal with triflic acid results in the formation of a mixture of species including U(OTf)4and leads to the reproducible isolation of the mononuclear U(IV) hydroxo complex [U(OTf)3(OH)(py)4] (1) and theU(IV) dinuclear 
-oxo-complex [{U(OTf)2(py)3}2{-O}{-OTf}2] (2). The X-ray crystal structures of these complexeshave been determined. Analytically pure complex 1 can be prepared in a 17-27% yield providing a good precursorfor the synthesis and study of the reactivity of the hydroxo complexes with different coordination environments.Two practical synthetic methods for the preparation of Lewis base adducts of U(OTf)3 are described. Analyticallypure [U(OTf)3(py)4] (4) was easily and reproducibly prepared (50-60% yield) by protonolysis of the amideU{N(SiMe3)2}3 with pyridinium triflate in pyridine. Salt metathesis of UI3(thf)4 with potassium triflate in acetonitrileresulted in the complete substitution of the iodide counterions by triflate producing the acetonitrile solvate [U(OTf)3(MeCN)3]n (3). The solid-state structure of 3 shows the formation of a unique U(III) coordination polymer in whichthe metal ions are connected by three triflates acting as bidentate bridging ligands to form a 1D chain.
-oxo-complex [{U(OTf)2(py)3}2{-O}{-OTf}2] (2). The X-ray crystal structures of these complexeshave been determined. Analytically pure complex 1 can be prepared in a 17-27% yield providing a good precursorfor the synthesis and study of the reactivity of the hydroxo complexes with different coordination environments.Two practical synthetic methods for the preparation of Lewis base adducts of U(OTf)3 are described. Analyticallypure [U(OTf)3(py)4] (4) was easily and reproducibly prepared (50-60% yield) by protonolysis of the amideU{N(SiMe3)2}3 with pyridinium triflate in pyridine. Salt metathesis of UI3(thf)4 with potassium triflate in acetonitrileresulted in the complete substitution of the iodide counterions by triflate producing the acetonitrile solvate [U(OTf)3(MeCN)3]n (3). The solid-state structure of 3 shows the formation of a unique U(III) coordination polymer in whichthe metal ions are connected by three triflates acting as bidentate bridging ligands to form a 1D chain.