Gröber Sebastian, Matczak Piotr, Domagała Sławomir, Weisheit Thomas, Görls Helmar, Düver Annika, Mlostoń Grzegorz, Weigand Wolfgang
Institute for Inorganic and Analytical Chemistry, Friedrich Schiller University Jena, Humboldstrasse 8, 07743 Jena, Germany.
Clinic of Nuclear Medicine, University Hospital Jena, Am Klinikum 1, 07747 Jena, Germany.
Materials (Basel). 2019 Sep 3;12(17):2832. doi: 10.3390/ma12172832.
Diferrocenyl thioketone reacts smoothly with (bisphosphane)Pt(0) complexes in toluene solution at room temperature yielding 1:1 adducts identified as ferrocenyl (Fc) functionalized platinathiiranes. Their structures were unambiguously confirmed by means of spectroscopic methods as well as by X-ray diffraction analysis. A unique, ferrocene-rich platinathiirane, bearing three Fc-units, was prepared starting with [bis(diphenylphosphino)ferrocene] Pt(0(-norbornene). For comparison, a similar platinathiirane with one Fc-unit was obtained from the reaction of the latter complex with thiobenzophenone. Quantum-chemical calculations were carried out to describe the bonding pattern and frontier molecular orbitals of the ferrocene-rich platinathiirane complexes. These calculations confirmed that the C=S bond loses its formally double-bond character upon complexation (bisphosphane)Pt(0). Cyclic voltammetry measurements were performed to characterize the obtained platinathiiranes in CHCl solutions. For comparison, the cyclic voltammogram for diferrocenyl thioketoneas a mixed-valent (Fe-Fe) compound was also recorded and analyzed. The results point out to a diffusion controlled electrode process in case of differocenyl thioketone and mixed diffusion and adsorption controlled electrode process in the case of the studied platinathiiranes.
二茂铁基硫酮在室温下于甲苯溶液中与（双膦）铂（0）配合物顺利反应，生成1:1加合物，鉴定为二茂铁基（Fc）官能化的铂硫杂环丙烷。通过光谱方法以及X射线衍射分析明确证实了它们的结构。以[双（二苯基膦基）二茂铁]铂（0）（降冰片烯）为起始原料，制备了一种独特的、富含二茂铁的铂硫杂环丙烷，其带有三个Fc单元。作为比较，通过后一种配合物与二苯甲酮硫醚的反应得到了一种具有一个Fc单元的类似铂硫杂环丙烷。进行了量子化学计算以描述富含二茂铁的铂硫杂环丙烷配合物的键合模式和前沿分子轨道。这些计算证实，在与（双膦）铂（0）络合后，C=S键失去了其形式上的双键特征。在CHCl溶液中进行循环伏安法测量以表征所得到的铂硫杂环丙烷。作为比较，还记录并分析了二茂铁基硫酮作为混合价（Fe-Fe）化合物的循环伏安图。结果表明，二茂铁基硫酮的情况是扩散控制的电极过程，而在所研究的铂硫杂环丙烷的情况下是混合扩散和吸附控制的电极过程。
