LAUSR

Abstract The reaction of XMg−CH2−Y−CH2−MgX [Y = 2,6−naphthylene (−C10H6−) or 1,1’−biphenylene (−C12H8−); X = Cl or Br] with two molar equivalents of Ph3SnCl or Ph2(Me3SiCH2)SnI gave Ph3Sn−CH2−C10H6−CH2−SnPh3 (1), Ph3Sn−CH2−C12H8−CH2−SnPh3 (2) and Ph2(Me3SiCH2)Sn−CH2−C12H8−CH2−Sn(CH2SiMe3)Ph2 (3), respectively, in good yields. Reaction of 2 with elemental iodine gave, via selective Sn-Ph bond cleavage, the corresponding bis(iododiphenylstannyl) derivative Ph2ISn−CH2−C12H8−CH2−SnIPh2 (4) and iodobenzene. Compounds 1–4 were characterized by spectroscopic methods, mass spectrometry and single-crystal X-ray diffraction analysis. The tin centers in 1−3 exhibit tetrahedral coordination geometries, both in solution and the solid state. For the bis(iododiphenylstannyl) derivative 4, the tin atoms show tetrahedral geometries only in solution, as deduced from the 119Sn NMR spectra. In the solid state, the metal atoms have distorted trigonal-bipyramidal environments as result of intermolecular I→Sn donor-acceptor interactions. In consequence, the crystal structure of 4 is composed of 2D coordination polymers, which are reinforced by C−H⋅⋅⋅I and C−H⋅⋅⋅π contacts.