Synthesis and characterisation of twelve SnIV diaryls and formation of a SnIII triaryl
作者:Peter B. Hitchcock、Michael F. Lappert、Luc J.-M. Pierssens、Andrey V. Protchenko、Patrick G. H. Uiterweerd
DOI:10.1039/b820835b
日期:——
Ten new crystalline compounds of formula (i) [Sn(ArN2)2(μ-E)}2] [E = O (2), S (3), Se (4), Te (5)], (ii) [Sn(ArN2)2(ER)2] [ER = SCH2Ph (6), SePh (7), TePh (8)], (iii) [Sn(ArN2)2(Br)R] [R = CH(SiMe3)2 (9), But (10)] and (iv) [Sn(ArN2)2CH(SiMe3)2}][BPh4] [ArN2 = C6H3(NMe2)2-2,6 (11)] have been prepared and identified by microanalysis, EI-mass spectrometry and multinuclear NMR spectroscopy, and for 2, 5, 6, 8 and 11 by single crystal X-ray diffraction. Whereas in the solid state, each of the latter five has only one of its two NMe2 substituents of each [ArN2]− ligand close to the tin atom (<3.1 Å), in solution at ambient temperature the NMe2 groups are characterised by a single 1H and 13C signal. The known compounds [Sn(ArN2)2(NCE)2] [E = O (12), S (13)] were synthesised by a new route: the redox reaction between [Sn(ArN2)2] (1) and 2AgNCE. Irradiation of a toluene solution of 1 at 298 K afforded a persistent radical assigned as [˙Sn(ArN2)3] (14).
十种新的结晶化合物式 (i) [Sn(ArN2)2(μ-E)}2] [E = O (2)、S (3)、Se (4)、Te (5)],(ii) [Sn(ArN2)2(ER)2] [ER = SCH2Ph (6)、SePh (7)、TePh (8)],(iii) [Sn(ArN2)2(Br)R] [R = CH(SiMe3)2 (9)、但 (10)] 和 (iv) [Sn(ArN2)2CH(SiMe3)2}][BPh4] [ArN2 = C6H3(NMe2)2-2,6 (11)] 已经制备完成,并通过显微分析、电离质谱法和多核核磁共振光谱法进行了鉴定,对 2、5、6、8 和 11 还进行了单晶 X 射线衍射鉴定。在固态下,后五种化合物中每种 [ArN2]- 配体的两个 NMe2 取代基中只有一个靠近锡原子(<3.1 Å),而在环境温度下的溶液中,NMe2 基团具有单一的 1H 和 13C 信号。已知化合物[Sn(ArN2)2(NCE)2] [E = O (12)、S (13)]是通过一种新方法合成的:[Sn(ArN2)2] (1) 与 2AgNCE 发生氧化还原反应。将 1 的甲苯溶液在 298 K 下辐照,可得到一种持久性自由基,命名为[˙Sn(ArN2)3] (14)。