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)

被引：10

作者：

Hildebrand, Alexandra ^{[1
,2
]}

Sarosi, Imola ^{[1
,2
]}

Loennecke, Peter ^{[2
]}

Silaghi-Dumitrescu, Luminita ^{[1
]}

Sarosi, Menyhart B. ^{[1
,2
]}

Silaghi-Dumitrescu, Ioan ^{[1
]}

Hey-Hawkins, Evamarie ^{[2
]}

机构：

[1] Univ Babes Bolyai, Dept Chem, RO-400084 Cluj Napoca, Romania

[2] Univ Leipzig, Inst Anorgan Chem, D-04103 Leipzig, Germany

来源：

DALTON TRANSACTIONS | 2012年 / 41卷 / 25期

关键词：

MOLECULAR-STRUCTURE; PHOSPHORUS-SULFUR; CRYSTAL-STRUCTURE; METAL-COMPLEXES; DENSITY FUNCTIONALS; CHELATE COMPLEXES; S-DEALKYLATION; BASIS-SETS; THIOLATE; METHYL;

D O I：

10.1039/c2dt00006g

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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 center dot 6H(2)O, Na-2[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)-kappa S-2,P}(2)] ([M{(BiphPS)-kappa S-2,P}(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 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)-mu-2-S-C6H4-kappa S-2,P)}(3)] (4) are also formed besides the mononuclear platinum bis-chelate complex 3.

引用

页码：7729 / 7736

页数：8

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