吡啶 、 (PhN=)WCl2(N,N'-bis(trimethylsilyl)-o-phenylenediamide) 在
Na 作用下,
以
四氢呋喃 为溶剂,
以91%的产率得到W(NPh)(o-(Me3SiN)2C6H4)bis(pyridine)
参考文献:
名称:
Coordinatively Unsaturated W(IV)−Bis(pyridine) Complexes, a Reactive Source of W(IV)
摘要:
Addition of 2 equiv of a a-donor ligand (L = pyridine, 4-picoline, or quinoline) to complexes of the type [W(NPh)-(eta (4)-arene)(o-(Me3SiN)(2)C6H4)] (arene = CH3CH2C6H5 (3), CH3CH2CH2C6H5 (4)) gave the W(IV)L-2 compounds, [W(NPh)(o-(Me3SiN)(2)C6H4)(C5H5N)(2)](5), [W(NPh)(o-(Me3SiN)(2)C6H4)(p-C6H7N)(2)](6), and [W(NPh)(o-(Me3SiN)(2)C6H4)(C9H7N)(2)] (7). Synthesis of compounds 5 and 6 by Na degrees reduction of [W(NPh)(o-(Me3SiN)(2)C6H4)Cl-2] in the presence of 3 equiv of L (L = 5, pyridine or 6, 4-picoline) is also presented. Compounds 5, 6, and 7 display hindered rotation of the donor ligands about the W-N bonds, resulting from a steric interaction with the Me3Si groups of the diamide ligand. The coordinative unsaturation of 5 and 6 has also been explored. Compounds 5 and 6 readily react with either CO and PMe3 to generated the six coordinate complexes [W(NPh)(o-(Me3SiN)(2)C6H4)(C5H5N)(2)(CO)] (8a), [W(NPh)(o-(Me3SiN)(2)C6H4)(C6H7N)(2)(CO)] (8b), [W(NPh)(o-(Me3SiN)(2)C6H4)(C5H5N)(PMe3)(2)] (10a), and [W(NPh)(o-(Me3SiN)(2)C6H4)(C6H7N)(PMe3)(2)] (10b), respectively.
Carbon–sulfur bond activation of thiophenes by [W(NPh){o-(Me3SiN)2C6H4}(pyridine)2]
作者:R. C. Mills、K. A. Abboud、J. M. Boncella
DOI:10.1039/b101955b
日期:——
Addition of thiophene, 2-methylthiophene, benzothiophene or
3-methylthiophene to
[W(NPh)o-(Me3SiN)2C6H
4}(C5H5N)2] 1 affords the
metallathiacycle complexes
[o-(Me3SiN)2C6H4
}(NPh)W(SC4H4)] 2,
[o-(Me3SiN)2C6H4
}(NPh)W(SC5H6)] 3,
[o-(Me3SiN)2C6H4
}(NPh)W(SC8H6)] 4 and
[o-(Me3SiN)2C6H4
}(NPh)W(SC5H6)] 5a and 5b, providing the
first example of thiophene CâS bond activation by a W(IV)
metal complex.