Novel mono- and bimetallic organotin(iv) compounds as potential linkers for coordination polymers.

Abstract

The reaction of [2-(O[double bond, length as m-dash]CH)C6H4]Me2SnCl (2), obtained by the hydrolysis of [2-{(CH2O)2CH}C6H4]Me2SnCl (1), with the appropriate diamine, in a 2 : 1 molar ratio, in the absence of a solvent or catalyst, resulted in the bimetallic species ClSnMe2[2-C6H4(4-CH[double bond, length as m-dash]N-1,1'-C6H4C6H4-4'-N[double bond, length as m-dash]CH)-2'-C6H4]Me2SnCl (4) and ClSnMe2[2-C6H4(CH[double bond, length as m-dash]NCH2CH2N[double bond, length as m-dash]CH)-2'-C6H4]Me2SnCl (5). The reaction of 2 and 5 with KSCN gave the corresponding isothiocyanates [2-(O[double bond, length as m-dash]CH)C6H4]Me2Sn(NCS) (3) and (SCN)SnMe2[2-C6H4(CH[double bond, length as m-dash]NCH2CH2N[double bond, length as m-dash]CH)-2'-C6H4]Me2Sn(NCS) (6). Treating 3 with H2NCH2CH2NH2 also resulted in the corresponding bimetallic compound 6. The reaction of 2 with sodium isonicotinate gave [2-(O[double bond, length as m-dash]CH)C6H4]Me2SnO(O)CC5H4N-4 (7) and the subsequent treatment with ZnTPP (TPP = tetraphenylporphyrinate) led to the isolation of the heterobimetallic complex [{2-(O[double bond, length as m-dash]CH)C6H4}Me2SnO(O)CC5H4N-4]ZnTPP (8). The compounds were characterized by multinuclear NMR spectroscopy and mass spectrometry in solution and IR spectroscopy in the solid state. The molecular structures for compounds 1-6 and 8 were established by single-crystal X-ray diffraction. For all compounds intramolecular O→Sn or Nimine→Sn coordination results in hypercoordinated species with a distorted trigonal bipyramidal (C,E)C2SnX core (E = O, Nimine; X = Cl, Nisothiocyanato, Oisonicotinato). In the heterobimetallic complex 8 the zinc atom has a distorted square pyramidal geometry with the Npyridyl atom at the apical position.