两种β-二亚胺锡化合物的合成与表征（英文）

Synthesis and Characterization of Two β-Diketiminato Tin(Ⅳ) Compounds

N,N-二(2,6-二异丙基苯基)-2,4-戊二亚胺的锂盐与二甲基二氯化锡的反应以及N,N-二(2,6-二乙基苯基)-2,4-戊二亚胺的锂盐与三甲基氯化锡的反应均以物质的量比为1∶1在室温下进行,分别得到了新化合物N(Ar)=C(Me)CH=C(NHAr)CH_2SnMe_2Cl·C_7H_8(1)(Ar=2,6-iPr_2C_6H_3)和[N(Ar')C(Me)=CHC(=NAr')CH_2SnMe_2]_2·CH_2Cl_2(2)(Ar'=2,6-Et_2C_6H_3).通常来说,β-二亚胺配体与金属卤化物反应容易形成氮-金属-氮键,而化合物1和2中由于SnMe_2Cl与SnMe_3基团的路易斯酸性使得锡-氮键断裂和锡-碳键的生成得到了少见的氮-锡-碳键.化合物2是罕见的具备两个共振结构式的锡二聚体.通过核磁共振、元素分析及X射线单晶衍射分析鉴定了这两种化合物的结构.通过这两个结构的对比探讨了二聚体2的形成机理.

The reactions of L1Li [Ll =HC（CMeNAr）2, Ar=2,6-iprzC6H3] with Me2SnC12, and LZLi [La=HC（CMeNAr＇）2, Ar＇=2,6-Et2C6H3] with Me3SnC1 in a molar ratio of l ： 1 were carried out at room temperature and acquired two new com- pounds, N（Ar）=C（Me）CH=C（NHAr）CH2SnMe2C1.C7H8 （1） and [N（Ar＇）C（Me）=CHC（=NAr＇）CH2SnMe2]2.CH2CI2 （2）, respectively. Different from regular nitrogen-metal-nitrogen bonds generated by the reactions of fl-diketiminato ligands with metal halides, uncommon nitrogen-tin-carbon bonds in compounds 1 and 2 were obtained by Sn--N bond cleavage and con- comitant Sn--C bond formation due to the Lewis acidity of SnMe3 and SnMe2C1 group. Compound 2 is a rare tin dimer with two resonant structures. Two compounds have been confirmed by 1H NMR, 13C NMR, elemental analysis, and single crystal X-ray structural analysis. Through the comparison of compounds 1 and 2, the formation mechanism of dimer 2 has been inves- tigated.