MeSi(CH(2)SnRO)(3) (R=Ph, Me(3)SiCH(2)): Building Blocks for Triangular‐Shaped Diorganotin Oxide Macrocycles

The syntheses of the novel silicon‐bridged tris(tetraorganotin) compounds MeSi(CH(2)SnPh(2)R)(3) (2, R=Ph; 5, R=Me(3)SiCH(2)) and their halogen‐substituted derivatives MeSi(CH(2)SnPh((3−n))I(n))(3) (3, n=1; 4, n=2) and MeSi(CH(2)SnI(2)R)(3) (6, R=Me(3)SiCH(2)) are reported. The reaction of compound 4 with di‐t‐butyltin oxide (t‐Bu(2)SnO)(3) gives the oktokaideka‐nuclear (18‐nuclear) molecular diorganotin oxide [MeSi(CH(2)SnPhO)(3)](6) (7) while the reaction of 6 with sodium hydroxide, NaOH, provides the trikonta‐nuclear (30‐nuclear) molecular diorganotin oxide [MeSi(CH(2)SnRO)(3)](10) (8, R=Me(3)SiCH(2)). Both 7 and 8 show belt‐like ladder‐type macrocyclic structures and are by far the biggest molecular diorganotin oxides reported to date. The compounds have been characterized by elemental analyses, electrospray mass spectrometry (ESI‐MS), NMR spectroscopy, (1)H DOSY NMR spectroscopy (7), IR spectroscopy (7, 8), and single‐crystal X‐ray diffraction analysis (2, 7, 8).