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