Synthesis and structures of new oligomethylene-bridged double ladders. How far can the layers be separated?

Abstract

The synthesis of the α,ω-bis[dichloro(trimethylsilylmethyl) stannyl]alkanes, (Me3SiCH2)Cl2Sn(CH 2) nSnCl2(CH2SiMe3) (13, n = 5; 14, n = 6; 15, n = 7; 16, n = 8; 17, n = 10; 18, n = 12) and the corresponding oligomethylene-bridged diorganotin oxides [(Me 3SiCH2)(O)Sn(CH2)nSn(O)(CH 2SiMe3)]m (19, n = 5; 20, n = 6; 21, n = 7; 22, n = 8; 23, n = 10; 24; n = 12) is reported. The reaction of the diorganodichlorostannanes 13-18 with the corresponding diorganotin oxides 19-24 provided the spacer-bridged tetraorganodistannoxanes {[(Me3SiCH 2)ClSn(CH2)nSnCl(CH2SiMe 3)]O}4 (25, n = 5; 26, n = 6; 27, n = 7; 28, n = 8; 29, n = 10; 30, n = 12). Compounds 13-30 have been identified by elemental analyses and multinuclear NMR spectroscopy. Compounds 25, 27, 29 and 30 have also been characterised by single crystal X-ray diffraction analysis and electrospray mass spectrometry. For the latter the essential double ladder motif is maintained for all n in the solid state, but subtle changes in alignment of the ladder planes occur. Separation between the two layers of the double ladder ranges from approx. 8.7 Å (for 25, n = 5) to approx. 15 Å (for 30, n = 12). In solution there is some dissociation of the double ladders into the corresponding dimers. The degree of dissociation is favoured by increasing oligomethylene chain length n.