Heteropolytopic phosphanylarylthiolato ligands: formation of cisisomers of nickel(ii), palladium(ii) and platinum(ii) complexes with 1-P(Biph)-2-SHC sub(6)H sub(4) (Biph = 1,1'-biphenyl-2,2'-diyl)

• Published in: Dalton transactions : an international journal of inorganic chemistry 2012-06, Vol.41 (25), p.7729-7736
• Main Authors: Hildebrand, Alexandra, Sarosi, Imola, Lonnecke, Peter, Silaghi-Dumitrescu, Luminita, Sarosi, Menyhart B, Silaghi-Dumitrescu, Ioan, Hey-Hawkins, Evamarie
• Format: Article
• Language: English
• Subjects: Density; Formations; Ligands; Mathematical analysis; Nickel; Palladium; Platinum; Stability
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c2dt00006g

Reaction of the ditopic phosphanylarylthiol 1-P(Biph)-2-SHC sub(6)H sub(4) (BiphPSH, Biph = 1,1'-biphenyl-2,2'-diyl), prepared by lithiation-electrophilic substitution, with NiCl sub(2).6H sub(2)O, Na sub(2)[PdCl sub(4)] and [PtI sub(2)(cod)] (cod = 1,5-cyclooctadiene) in a 2 : 1 ratio and in the presence of NEt sub(3) led to formation of exclusively cisisomers of the square-planar complexes cis-[M{(1-P(Biph)-2-S-C sub(6)H sub(4))- Kappa super(2) S,P} sub(2)] ([M{(BiphPS)- Kappa super(2)S,P} sub(2)]; M = Ni (1), Pd (2), Pt (3)). Density functional calculations support the assumption that this is probably due to intramolecular pi - pi interaction of the biphenyl groups, which results in enhanced stability of the cisisomers. 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)- mu -2-S-C sub(6)H sub(4 )- Kappa super(2)S, P)} sub(3)] (4) are also formed besides the mononuclear platinum bis-chelate complex 3.