Heteropolytopic arsanylarylthiolato ligands: cis-trans isomerism of nickel(II), palladium(II), and platinum(II) complexes of 1-AsPh2-2-SHC6H4 |
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Authors: | Hildebrand Alexandra Sárosi Imola Lönnecke Peter Silaghi-Dumitrescu Luminiţa Sárosi Menyhárt B Silaghi-Dumitrescu Ioan Hey-Hawkins Evamarie |
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Affiliation: | Faculty of Chemistry and Chemical Engineering, Babe?-Bolyai University, Kogalniceanu 1, RO-400084 Cluj-Napoca, Romania. |
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Abstract: | Heteropolytopic arsanylthiolato ligands 1-AsPh(2)-2-SHC(6)H(4) (AsSH), PhAs(2-SHC(6)H(4))(2) (AsS(2)H(2)), and As(2-SHC(6)H(4))(3) (AsS(3)H(3)) have been prepared by lithiation-electrophilic substitution procedures. The 2:1 reaction of AsSH with NiCl(2)·6H(2)O, Na(2)[PdCl(4)], and [PtI(2)(cod)] (cod = 1,5-cyclooctadiene) in the presence of NEt(3) afforded the square-planar complexes trans-[Ni{(AsS)-κ(2)S,As}(2)] (1), cis-[Pd{(AsS)-κ(2)S,As}(2)] (2), trans-[Pd{(AsS)-κ(2)S,As}(2)] (3), and cis-[Pt{(AsS)-κ(2)S,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-AsPh(2)-μ-2-S-C(6)H(4)-κ(2)S,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. |
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