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Issue 25, 2012
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Heteropolytopic phosphanylarylthiolato ligands: formation of cis isomers of nickel(ii), palladium(ii) and platinum(ii) complexes with 1-P(Biph)-2-SHC6H4 (Biph = 1,1′-biphenyl-2,2′-diyl)

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Abstract

Reaction of the ditopic phosphanylarylthiol 1-P(Biph)-2-SHC6H4 (BiphPSH, Biph = 1,1′-biphenyl-2,2′-diyl), prepared by lithiation–electrophilic substitution, with NiCl2·6H2O, Na2[PdCl4] and [PtI2(cod)] (cod = 1,5-cyclooctadiene) in a 2 : 1 ratio and in the presence of NEt3 led to formation of exclusively cis isomers of the square-planar complexes cis-[M{(1-P(Biph)-2-S-C6H4)-κ2S,P}2] ([M{(BiphPS)-κ2S,P}2]; M = Ni (1), Pd (2), Pt (3)). Density functional calculations support the assumption that this is probably due to intramolecular π–π interaction of the biphenyl groups, which results in enhanced stability of the cis isomers. Compound 1 is the first example of a structurally characterised mononuclear cis-bis(phosphanylthiolato)nickel(II) complex. Small amounts of the trinuclear complex [{PtI(1-P(Biph)-μ-2-S-C6H42S,P)}3] (4) are also formed besides the mononuclear platinum bis-chelate complex 3.

Graphical abstract: Heteropolytopic phosphanylarylthiolato ligands: formation of cis isomers of nickel(ii), palladium(ii) and platinum(ii) complexes with 1-P(Biph)-2-SHC6H4 (Biph = 1,1′-biphenyl-2,2′-diyl)

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Supplementary files

Article information


Submitted
02 Jan 2012
Accepted
30 Apr 2012
First published
01 May 2012

Dalton Trans., 2012,41, 7729-7736
Article type
Paper

Heteropolytopic phosphanylarylthiolato ligands: formation of cis isomers of nickel(II), palladium(II) and platinum(II) complexes with 1-P(Biph)-2-SHC6H4 (Biph = 1,1′-biphenyl-2,2′-diyl)

A. Hildebrand, I. Sárosi, P. Lönnecke, L. Silaghi-Dumitrescu, M. B. Sárosi, I. Silaghi-Dumitrescu and E. Hey-Hawkins, Dalton Trans., 2012, 41, 7729
DOI: 10.1039/C2DT00006G

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