Tetranuclear organometallic complexes based on 1,2-ethanedithiolate ligands as potential precursors for CuMS2 (M = Ga, In)
作者:Dirk Friedrich、Oliver Kluge、Marcus Kischel、Harald Krautscheid
DOI:10.1039/c3dt50461a
日期:——
The synthesis and characterization of a series of homologous tetranuclear complexes [(iPr3PCu)2(MR2)2(SCH2CH2S)2] (MR2 = GaMe2 (2), GaEt2 (3), GaiPr2 (4), GanBu2 (5) and InMe2 (6), InEt2 (7), IniPr2 (8), InnBu2 (9)) and of related compounds [(iPr3PCu)3(MR2)(SCH2CH2S)2] (MR2 = GaMe2 (10), GaEt2 (11), GaiPr2 (12), GanBu2 (13) and InMe2 (14), InEt2 (15), IniPr2 (16), InnBu2 (17)) are presented. The molecular structures of these were determined by single crystal X-ray diffraction. Thermolysis processes of all the representatives of 2–9 were investigated by simultaneous thermal analysis and thermal decomposition in a nitrogen atmosphere in a quartz glass tube. According to powder X-ray diffraction studies these thermolysis residues predominantly consist of CuMS2 (M = Ga, In), which mainly occurred in the well known tetragonal chalcopyrite-type structure and partially in the hexagonal wurtzite-type structure. As expected from their composition, representatives of 10–17 form mixtures of CuMS2 and large amounts of Cu2−xS upon thermolysis.
一系列同源四核配合物 [(iPr3PCu)2(MR2)2(SCH2CH2S)2] (MR2 = GaMe2 (2)、GaEt2 (3)、GaiPr2 (4)、GanBu2 (5) 和 InMe2 ( 6)、InEt2 (7)、IniPr2 (8)、InnBu2 (9)) 及相关化合物[(iPr3PCu)3(MR2)(SCH2CH2S)2] (MR2 = GaMe2 (10)、GaEt2 (11)、GaiPr2 (12)、GanBu2 (13) 和 InMe2 (14)、InEt2 (15)、IniPr2 (16) ,InnBu2 (17)) 被提出。通过单晶X射线衍射确定了它们的分子结构。通过在石英玻璃管中的氮气气氛中同时进行热分析和热分解,研究了 2-9 的所有代表的热解过程。根据粉末X射线衍射研究,这些热解残留物主要由CuMS2(M = Ga,In)组成,其主要出现在众所周知的四方黄铜矿型结构中,部分出现在六方纤锌矿型结构中。正如从其组成中所预期的那样,10-17 的代表在热解时形成 CuMS2 和大量 Cu2−xS 的混合物。