High-Coordinate Gold(I) Complexes with Dithiocarboxylate Ligands

详细信息    查看全文

• 作者：Christoph Kaub ; Timo Augenstein ; Thomas O. Bauer ; Elisa Rothe ; Lars Esmezjan ; Volker Sch眉nemann ; Peter W. Roesky
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：May 5, 2014
• 年：2014
• 卷：53
• 期：9
• 页码：4491-4499
• 全文大小：381K
• 年卷期：v.53,no.9(May 5, 2014)
• ISSN：1520-510X

文摘

Ferrocene dithiocarboxylate has been introduced into the chemistry of gold(I) and copper(I). First, a modified synthesis of piperidinium ferrocene dithiocarboxylate (1) is reported. Reaction of this reagent with [Au(tht)Cl] in the presence of different phosphines resulted in monomeric, dimeric, and polymeric structures. Although gold(I) is usually two coordinate, mainly three- and four-fold coordinated compounds were obtained by using ferrocene dithiocarboxylate as ligands. The isolated compounds are [(FcCSS)Au(PPh₃)₂] (2) (FcCSS = ferrocene dithiocarboxylate), [(FcCSS)Au₂(dppm)₂] (3) (dppm = bis(diphenylphosphino)methane), and [(FcCSS)Au(dppf)]_n (4) (dppf = bis(diphenylphosphino)ferrocene) [{(FcCSS)Au}₂(dppp)] (5) (dppp = bis(diphenylphosphino)propane). The FcCSS ligand shows a remarkable flexible coordination mode. It coordinates either in a monodentate, a chelating, or in a metal bridging mode. In the four gold(I) complexes 2鈥?b>5 four different coordination modes of the FcCSS ligand are seen. Attempts to extend this rich coordination chemistry to other coinage metals were only partly successful. [(FcCSS)Cu(PPh₃)₂] (6) was obtained from the reaction of piperidinium ferrocene dithiocarboxylate with [(Ph₃P)₃CuCl]. ⁵⁷Fe鈥揗枚ssbauer spectroscopy was performed for compounds 2鈥?b>4. The spectra show isomer shifts and quadrupole splittings that are typical for diamagnetic ferrocenes.