Heteropolytopic Arsanylarylthiolato Ligands: Cis鈥揟rans Isomerism of Nickel(II), Palladium(II), and Platinum(II) Complexes of 1-AsPh2-2-SHC6H4

详细信息    查看全文

• 作者：Alexandra Hildebrand ; Imola S谩rosi ; Peter L枚nnecke ; Lumini牛a Silaghi-Dumitrescu ; Menyh谩rt B. S谩rosi ; Ioan Silaghi-Dumitrescu ; Evamarie Hey-Hawkins
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：July 2, 2012
• 年：2012
• 卷：51
• 期：13
• 页码：7125-7133
• 全文大小：435K
• 年卷期：v.51,no.13(July 2, 2012)
• ISSN：1520-510X

文摘

Heteropolytopic arsanylthiolato ligands 1-AsPh₂-2-SHC₆H₄ (AsSH), PhAs(2-SHC₆H₄)₂ (AsS₂H₂), and As(2-SHC₆H₄)₃ (AsS₃H₃) have been prepared by lithiation鈥揺lectrophilic substitution procedures. The 2:1 reaction of AsSH with NiCl₂路6H₂O, Na₂[PdCl₄], and [PtI₂(cod)] (cod = 1,5-cyclooctadiene) in the presence of NEt₃ afforded the square-planar complexes trans-[Ni{(AsS)-魏²S,As}₂] (1), cis-[Pd{(AsS)-魏²S,As}₂] (2), trans-[Pd{(AsS)-魏²S,As}₂] (3), and cis-[Pt{(AsS)-魏²S,As}₂] (4). In the cases of nickel and platinum, only one isomer was isolated. With palladium, initially the cis isomer 2 is formed and undergoes slow isomerization to the trans isomer 3 in solution. Small amounts of the trinuclear complex [{PtI(1-AsPh₂-渭-2-S-C₆H₄-魏²S,As)}₃] (5) are also formed besides the mononuclear platinum bis-chelate complex 4. Density functional theory calculations support a dissociative mechanism for the isomerization of the palladium(II) complexes.