Metal-phosphine chalcogenide interactions. Crystal structures of palladium(II)/mercury(II) complexes with 1,2-bis(diphenylthiophosphinyl)ethane containing seven-membered metallacyclic rings

摘要

An organophosphorus ligand, namely, 1,2-bis(diphenylthiophosphinyl)ethane {Ph2P(S)-CH2-CH2-P(S)Ph-2; dppeS(2)} reacted with palladium(II) chloride in acetonitrile forming [PdCl2(dppeS(2))](CH3CN) (1). Similarly, it reacted with mercury(II) bromide in acetone to yield HgBr2(dppeS(2)) (2). In these compounds, Pd/Hg are bonded to two S atoms of chelating dppeS(2) ligand and to the respective halogen atoms. The geometry about Pd is distorted square planar with trans-bond angles S(1)-Pd-Cl(1) and S(2)- Pd-Cl(2) being 174.10(5)degrees and 172.85(5)degrees, respectively. The angles about Hg vary in the range 96.20(6)-124.56(4)degrees, suggesting highly distorted geometry about Hg. The bite angle S(1)-Hg-S(2) of the ligand is 118.85degrees in 2 versus 97.76degrees in 1, and it demonstrates large flexibility of alkane moiety and stability of the seven-membered metallacyclic rings formed by dppeS(2). (C) 2002 Elsevier Science Ltd. All rights reserved. [References: 39]