Ahmet Ibrahim Y, Hill Michael S, Raithby Paul R, Johnson Andrew L
Centre for Sustainable Chemical Technologies, Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
Centre for Sustainable Chemical Technologies, Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK and Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
Dalton Trans. 2018 Apr 3;47(14):5031-5048. doi: 10.1039/C8DT00773J.
A family of tin(ii) guanidinate complexes of the general form [{RNC(NMe2)NR}2Sn] (R = iPr (6), Cy (7), Tol (9) and Dipp (10)) and [{tBuNC(NMe2)NtBu}Sn{NMe2}] (8) have been synthesised and isolated from the reaction of tin(ii) bis-dimethylamide and a series of carbodiimides (1-5). The cyclic poly-chalcogenide compounds [{CyNC(NMe2)NCy}2Sn{Chx}] (Ch = S, x = 4 (11); Ch = Se, x = 4 (12), and Ch = S, x = 6 (13)) with {SnChx} rings were prepared by the oxidative addition of elemental sulfur and selenium to the heteroleptic stannylene complex [{CyNC(NMe2)NCy}2Sn] (7) in THF at room temperature. Similarly, reaction of compounds 6 and 7 with an equimolar amount of the chalcogen transfer reagents (SC3H6 and Se[double bond, length as m-dash]PEt3, respectively) led to the formation of the chalcogenide tin(iv) complexes [{RNC(NMe2)NR}Sn(Ch)] (R = Cy: Ch = S (14); R = iPr, Ch = Se (15); R = Cy, Ch = Se (16)) with terminal Sn[double bond, length as m-dash]Ch (14 and 16) and dimeric bridged seleno-tin {Sn2Se2} rings (15), respectively. The mono telluro-compounds [{RNC(NMe2)NR}Sn(Te)] (R = iPr (17); R = Cy (18)) were similarly prepared by the oxidative addition of elemental tellurium to 7 and 8, respectively. All of the tin containing compounds have been investigated by multinuclear NMR (1H, 13C 119Sn and 77Se/125Te, where possible), elemental analysis and single crystal X-ray structural analysis (7, 8, 10-13, 15-18). Thermogravimetric analysis (TGA) was used to probe the possible utility of complexes 6-8, 11-12 and 14-18 as single source Sn and SnCh precursors. The Sn(ii) compounds 6 and 7 have been utilised in the growth of thin films by aerosol-assisted chemical vapor deposition (AACVD) at both 300 and 400 °C. The thin films have been analysed by pXRD, EDS, SEM and AFM and shown to be Sn metal. Subsequent studies provided film growth at temperatures as low as 200 °C. Similarly, the mono-chalcogenide systems 14, 16 and 18 have been utilised in the AACVD of thin films. These latter studies provided films, grown at 300 and 400 °C, which have also been analysed by pXRD, Raman spectroscopy, AFM, and SEM and are shown to comprise phase pure SnS, SnSe and SnTe, respectively. These preliminary results demonstrate the potential of such simple guanidinate complexes to act as single source precursors with a high degree of oxidative control over the deposited thin films.
通过二甲基锡（II）双酰胺与一系列碳二亚胺（1 - 5）反应，合成并分离得到了通式为[{RNC(NMe2)NR}2Sn]（R = iPr (6)、Cy (7)、Tol (9) 和 Dipp (10)）以及[{tBuNC(NMe2)NtBu}Sn{NMe2}]（8）的胍基锡（II）配合物家族。通过在室温下，于四氢呋喃（THF）中，将元素硫和硒氧化加成到杂配亚锡烯配合物[{CyNC(NMe2)NCy}2Sn]（7）上，制备了含{SnChx}环的环状多硫属化物化合物[{CyNC(NMe2)NCy}2Sn{Chx}]（Ch = S，x = 4 (11)；Ch = Se，x = 4 (12)，以及Ch = S，x = 6 (13)）。类似地，化合物6和7分别与等摩尔量的硫属转移试剂（分别为SC3H6和Se═PEt3）反应，生成了硫属化物锡（IV）配合物[{RNC(NMe2)NR}Sn(Ch)]（R = Cy：Ch = S (14)；R = iPr, Ch = Se (15)；R = Cy, Ch = Se (16)），分别具有末端Sn═Ch（14和16）和二聚桥联硒锡{Sn2Se2}环（15）。通过分别将元素碲氧化加成到7和8上，类似地制备了单碲化合物[{RNC(NMe2)NR}Sn(Te)]（R = iPr (17)；R = Cy (18)）。所有含锡化合物均通过多核NMR（1H、13C、119Sn以及可能的77Se/125Te）、元素分析和单晶X射线结构分析（7、8、10 - 13、15 - 18）进行了研究。热重分析（TGA）用于探究配合物6 - 8, 11 - 12和14 - 18作为单源Sn和SnCh前驱体的可能用途。锡（II）化合物6和7已用于在300和400°C下通过气溶胶辅助化学气相沉积（AACVD）生长薄膜。通过粉末X射线衍射（pXRD）、能谱分析（EDS）、扫描电子显微镜（SEM）和原子力显微镜（AFM）对薄膜进行分析，结果表明其为金属锡。后续研究表明在低至200°C的温度下也能实现薄膜生长。类似地，单硫属化物体系14、16和18已用于AACVD制备薄膜。这些后续研究得到了在300和400°C下生长的薄膜，通过pXRD、拉曼光谱、AFM和SEM分析表明，它们分别由相纯的SnS、SnSe和SnTe组成。这些初步结果证明了此类简单胍基配合物作为单源前驱体的潜力，能够对沉积薄膜进行高度的氧化控制。
