کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1627595 | 1516455 | 2006 | 6 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Synthesis of actinide η2-pyridyl and η2-α-picolyl complexes by carbon–hydrogen bond activation Synthesis of actinide η2-pyridyl and η2-α-picolyl complexes by carbon–hydrogen bond activation](/preview/png/1627595.png)
Studies in our laboratory have shown that the thorium(IV) complexes (C5Me5)2ThPh2 and (C5Me5)2Th(CH2Ph2)2 mediate carbon–nitrogen bond cleavage and dearomatization of the pyridine ring in pyridine N-oxide. Based upon these results, we examined the analogous chemistry with a variety of pyridine compounds to determine if the electron-withdrawing oxygen present in pyridine N-oxide was required for reactivity of this type. Interestingly, reaction of (C5Me5)2An(CH3)2 (An = Th, U) with pyridine and substituted analogues produces CH4 and the corresponding η2-(N,C)-pyridyl complexes by activation of the sp2-hybridized ortho C–H bond. Isotopic labeling studies indicate that the C–H activation reactions are consistent with a σ-bond metathesis mechanism. Additionally, the η2-(N,C)-pyridyl complexes undergo ligand-exchange reactions with both pyridine-d5 and α-picoline.
Journal: Journal of Alloys and Compounds - Volume 418, Issues 1–2, 20 July 2006, Pages 178–183