CS2在Ag-S键中的插入反应的研究(PPh3)2 Ag(S2CSBu^t)

白色的[Bu^tSAg]nPPh3溶于CS2中, 析出桔黄色晶体. 经X射线单晶结构分析其结构为(PPh3)2Ag(S2CSBu^t). 发现了一个CS2在Ag-S键中的插入反应. 此反应为可逆反应, 晶体在120-130℃失去CS2. 晶体属三斜晶系, 空间群P1,a=10.571(1), b=13.638(3), c=14.391(3)A, α=88.75(2), β=72.84(1), γ=80.58(1)°, V=1954.9A^3, Dc=1.36g/cm^3, Dm=1.36g/cm^3, Z=2. 3572个衍射点参与修正, R=0.045, Rw=0.043, Ag原子以变形四面体与硫代黄原酸配体Bu^tS-CS2的两个S原子及两个PPh3的P原子配位. 插入反应形成的CS3基团基本上共面, 其C-S键长比CS2中的键长明显加长, 而比单键的C-S键长要短, 并在红外光谱上出现特征吸收峰.

Insertion reaction of CS2 into Ag-S bond synthesis and crystal structure of (PPh3)2 Ag(S2CSBu^t)

Colorless (Me3CSAg)n and PPh3 was dissolved in CS2, to give orange crystalline (PPh3)2Ag(S2CSCMe3) which was characterized by single crystal x-ray diffraction. The reaction constitutes a novel insertion reaction of CS2 into Ag-S bond. The reaction was reversible, CS2 lost at 120-130? The crystal is triclinic, space group P1, a 10.571(1), b 13.638(3), c 14.391(3) ? a 88.75(2), b 72.84(1), g 80.58(1)? Z = 2, dc = 1.36, do = 1.36 g/cm3, R = 0.0454, and Rw = 0.043. The Ag atom is pseudotetrahedrally coordinated by 2 S atoms of Me3CSCS2, and 2 P. The CS3 group resulting from insertion of CS2 into Ag-S bond is approx. planar. The C-S bond lengths of CS3 are longer than that of uncoordinated CS2 and shorter than the single-bond length. Its IR spectrum was determine