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

Alexandra Hildebrand; Imola Sárosi; Peter Lönnecke; Luminiţa Silaghi-Dumitrescu; Menyhárt B Sárosi; Ioan Silaghi-Dumitrescu; Evamarie Hey-Hawkins

doi:10.1039/c2dt00006g

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

Dalton Trans. 2012 Jul 7;41(25):7729-36. doi: 10.1039/c2dt00006g. Epub 2012 May 23.

Authors

Alexandra Hildebrand¹, Imola Sárosi, Peter Lönnecke, Luminiţa Silaghi-Dumitrescu, Menyhárt B Sárosi, Ioan Silaghi-Dumitrescu, Evamarie Hey-Hawkins

Affiliation

¹ Department of Chemistry, Babeş-Bolyai University, Kogalniceanu 1, RO-400084 Cluj-Napoca, Romania.

PMID: 22622156
DOI: 10.1039/c2dt00006g

Abstract

Reaction of the ditopic phosphanylarylthiol 1-P(Biph)-2-SHC(6)H(4) (BiphPSH, Biph = 1,1'-biphenyl-2,2'-diyl), prepared by lithiation-electrophilic substitution, with NiCl(2)·6H(2)O, Na(2)[PdCl(4)] and [PtI(2)(cod)] (cod = 1,5-cyclooctadiene) in a 2:1 ratio and in the presence of NEt(3) led to formation of exclusively cis isomers of the square-planar complexes cis-[M{(1-P(Biph)-2-S-C(6)H(4))-κ(2)S,P}(2)] ([M{(BiphPS)-κ(2)S,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(III) complex. Small amounts of the trinuclear complex [{PtI(1-P(Biph)-μ-2-S-C(6)H(4)-κ(2)S,P)}(3)] (4) are also formed besides the mononuclear platinum bis-chelate complex 3.