کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1341030 | 979767 | 2006 | 14 صفحه PDF | دانلود رایگان |
[Me2Si(C5Me4)2]MoH2 reacts with furan and benzofuran to yield products resulting from C–H bond cleavage, namely [Me2Si(C5Me4)2]Mo(η1-C-C4H3O)H and [Me2Si(C5Me4)2]Mo(η1-C-C8H5O)H, whereas the corresponding reactions of selenophene and benzoselenophene yield products resulting from C–Se bond cleavage, namely [Me2Si(C5Me4)2]Mo(η2-C,Se-SeC4H4) and [Me2Si(C5Me4)2]Mo(η2-C,Se-SeC8H6). On this basis, the reactivity of the selenophene derivatives is analogous to that of previously reported thiophene derivatives, while the reactivity of the furan derivatives is unique. DFT calculations indicate that C–E (E = O, S, Se) bond cleavage is thermodynamically more favored than C–H bond cleavage for each of the chalcogen derivatives. As such, the calculations provide evidence that C–O bond cleavage of the furan derivatives is not observed because of kinetic factors. DFT calculations also demonstrate that the observation of C–S bond cleavage of thiophene by the ansa metallocene [Me2Si(C5Me4)2]MoH2 and C–H bond cleavage by Cp2MoH2 is dictated by thermodynamic factors. Specifically, the Me2Si ansa bridge thermodynamically favors [Me2Si(C5Me4)2]Mo(η2-C,S-SC4H4) over [Me2Si(C5Me4)2]Mo(η1-C-SC4H3)H because the bridge promotes a shift in the coordination of the cyclopentadienyl rings from η5-coordination towards η3-coordination and this thermodynamically unfavorable modification is stabilized by sulfur-to-metal π-donation within [Me2Si(C5Me4)2]Mo(η2-C,S-SC4H4).
[Me2Si(C5Me4)2]MoH2 reacts with furan to yield a product resulting from C–H bond cleavage, namely [Me2Si(C5Me4)2]Mo(η1-C-C4H3O)H, whereas the corresponding reactions of thiophene and selenophene yield products resulting from C–S and C–Se bond cleavage, namely [Me2Si(C5Me4)2]Mo(η2-C,S-SC4H4) and [Me2Si(C5Me4)2]Mo(η2-C,Se-SeC4H4).Figure optionsDownload as PowerPoint slide
Journal: Polyhedron - Volume 25, Issue 2, 23 January 2006, Pages 499–512