title: 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).
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.
authors.affiliation: Department of Chemistry, Babeş-Bolyai University, Kogalniceanu 1, RO-400084 Cluj-Napoca, Romania.
authors.forename: Alexandra
authors.initials: A
authors.lastname: Hildebrand
authors.forename: Imola
authors.initials: I
authors.lastname: Sárosi
authors.forename: Peter
authors.initials: P
authors.lastname: Lönnecke
authors.forename: Luminiţa
authors.initials: L
authors.lastname: Silaghi-Dumitrescu
authors.forename: Menyhárt B
authors.initials: MB
authors.lastname: Sárosi
authors.forename: Ioan
authors.initials: I
authors.lastname: Silaghi-Dumitrescu
authors.forename: Evamarie
authors.initials: E
authors.lastname: Hey-Hawkins