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

被引：16

作者：

Hildebrand, Alexandra ^{[1
,2
]}

Sarosi, Imola ^{[1
,2
]}

Loennecke, Peter ^{[2
]}

Silaghi-Dumitrescu, Luminita ^{[1
]}

Sarosi, Menyhart B. ^{[1
,2
]}

Silaghi-Dumitrescu, Ioan ^{[1
]}

Hey-Hawkins, Evamarie ^{[2
]}

机构：

[1] Univ Babes Bolyai, Fac Chem & Chem Engn, RO-400084 Cluj Napoca, Romania

[2] Univ Leipzig, Inst Anorgan Chem, D-04103 Leipzig, Germany

来源：

INORGANIC CHEMISTRY | 2012年 / 51卷 / 13期

关键词：

CRYSTAL-STRUCTURE; MOLECULAR-STRUCTURE; PHOSPHORUS-SULFUR; METAL-COMPLEXES; S-DEALKYLATION; COORDINATION CHEMISTRY; DENSITY FUNCTIONALS; CARBONYL-COMPLEXES; CHELATE COMPLEXES; STILLE REACTION;

D O I：

10.1021/ic300002p

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Heteropolytopic arsanylthiolato ligands 1-AsPh2-2-SHC6H4. (AsSH), PhAs(2-SHC6H4)(2) (AsS2H2), and As(2-SHC6H4)(3) (AsS3H3) have been prepared by lithiation-electrophilic substitution procedures. The 2:1 reaction of AsSH with NiCl2 center dot 6H(2)O, Na-2[PdCl4], and [PtI2(cod)] (cod = 1,5-cyclooctadiene) in the presence of NEt3 afforded the square-planar complexes trans-[Ni{(AsS)-kappa S-2,As}(2)] (1), cis-[Pd{(AsS)-kappa S-2,As}(2)] (2), trans-[Pd{(AsS)-kappa S-2,As}(2)] (3), and cis-[Pt{(AsS)-kappa S-2,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-p-2-S-C6H4-kappa S-2,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.

引用

页码：7125 / 7133

页数：9

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