Silicon- and Tin-Containing Open-Chain and Eight-Membered-Ring Compounds as Bicentric Lewis Acids toward Anions.

Herein, we report the syntheses of silicon- and tin-containing open-chain and eight-membered-ring compounds Me2 Si(CH2 SnMe2 X)2 (2, X=Me; 3, X=Cl; 4, X=F), CH2 (SnMe2 CH2 I)2 (7), CH2 (SnMe2 CH2 Cl)2 (8), cyclo-Me2 Sn(CH2 SnMe2 CH2 )2 SiMe2 (6), cyclo-(Me2 SnCH2 )4 (9), cyclo-Me(2-n) Xn Sn(CH2 SiMe2 CH2 )2 SnXn Me(2-n) (5, n=0; 10, n=1, X=Cl; 11, n=1, X=F; 12, n=2, X=Cl), and the chloride and fluoride complexes NEt4 [cyclo- Me(Cl)Sn(CH2 SiMe2 CH2 )2 Sn(Cl)Me⋅F] (13), PPh4 [cyclo-Me(Cl)Sn(CH2 SiMe2 CH2 )2 Sn(Cl)Me⋅Cl] (14), NEt4 [cyclo-Me(F)Sn(CH2 SiMe2 CH2 )2 Sn(F)Me⋅F] (15), [NEt4 ]2 [cyclo-Cl2 Sn(CH2 SiMe2 CH2 )2 SnCl2 ⋅2 Cl] (16), M[Me2 Si(CH2 Sn(Cl)Me2 )2 ⋅Cl] (17 a, M=PPh4 ; 17 b, M=NEt4 ), NEt4 [Me2 Si(CH2 Sn(Cl)Me2 )2 ⋅F] (18), NEt4 [Me2 Si(CH2 Sn(F)Me2 )2 ⋅F] (19), and PPh4 [Me2 Si(CH2 Sn(Cl)Me2 )2 ⋅Br] (20). The compounds were characterised by electrospray mass-spectrometric, IR and (1) H, (13) C, (19) F, (29) Si, and (119) Sn NMR spectroscopic analysis, and, except for 15 and 18, single-crystal X-ray diffraction studies.

Syntheses, Structures, and Complexation Studies of Tris(organostannyl)methane Derivatives.

The syntheses of tris(organostannyl)methanes HC(SnX n Ph(3-n))3 (1, n=0; 2, n=1, X=I; 3, n=1, X =F; 4, n=1, X=Cl; 5, n=1, X=OAc; 6, n=2, X=I; 7, n=2, X=Cl) and the organostannate complexes Et4N[HC(SnIPh2)3⋅F] (8), Ph4P[HC(SnClPh2)3⋅Cl] (9), and [Ph4P]2[HC(SnCl2Ph)3⋅2 Cl] (10) are reported. The compounds were characterized by 1H, 13C, 19F, and 119Sn NMR spectroscopy, IR spectroscopy, electrospray mass spectrometry, and (with the exception of 3) single-crystal X-ray diffraction analysis. From the reaction between 2 and AgClO4 resulted the unprecedented hexanuclear organotin oxocluster [HC{Sn(ClO4)2Ph2}2Sn(OH)2Ph]2 (11), the molecular structure of which was elucidated by using X-ray crystallography.