文摘
A novel one-pot approach to synthesize the tiara-like Pd(II) thiolate complex compound, [Pd(SCH3)2]6 was developed. In this strategy, dimethyl sulfoxide (DMSO) was used as a thiolate source instead of methyl mercaptan (CH3SH). DMSO was first decomposed into CH3SH and formaldehyde (HCHO); then, the in situ as-formed CH3SH molecules reacted with palladium acetate, and formed [Pd(SCH3)2]6. By tuning the reaction condition, the morphology of the [Pd(SCH3)2]6 assemblies can change from microprism to nanosphere. The characterization of the pyrolysis product demonstrated that these two kinds of [Pd(SCH3)2]6 assemblies with different shapes could further decompose into palladium or palladium sulfides through different pyrolysis conditions. 中文摘要 本文以醋酸钯为钯源, 二甲基亚砜为硫源, 在乙二醇和醋酸存在的条件下通过一步法制备了一种六核钯–甲硫醇团簇化合物 [Pd(SCH3)2]6. 其具有特征的类花冠形结构. 对其反应机制进行了探讨, 首先二甲基亚砜分解生成甲硫醇和甲醛, 钯与甲硫醇反应原位生 成钯–甲硫醇团簇. 这些生成的团簇分子进一步组装成微米尺寸大小的棱柱. 通过向反应体系中引入一种表面活性剂, 产物的形貌从微 米棱柱转变为纳米球. 350°C下, [Pd(SCH3)2]6的微米棱柱在空气中分解得到金属钯单质. 对其热解产物进行电镜表征, 发现其在保持原 有棱柱形貌的基础上形成了孔道结构. 在不同的热解条件下可以得到钯或硫化钯热解产物.