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Synthesis, X-ray diffraction analysis and multinuclear NMR study of (Z)-3,4,4-trimethyl-1-triphenylstannyl-1-pentene-3-ol and its monoiodinated derivative

par Kayser, François;Biesemans, Monique;Delmotte, André ;Verbruggen, I;De Borger, I.;Gielen, Marcel ;Willem, Rudolph ;Tiekink, Edward
Référence Organometallics, 13, page (4026-4032)
Publication Publié, 1994

Article révisé par les pairs

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Résumé :

The syntheses of (Z)-3,4,4-trimethyl-1-(triphenylstannyl)-1-pentene-3-ol (1) and (Z)-3,4,4-trimethyl-1-(iododiphenylstannyl)-1-penten-3-ol (2) are reported. The solid-state structures of these tetra- and triorganotin compounds were determined by X-ray diffraction methods. The tin atom in 1 exists in a tetrahedral geometry distorted toward a trigonal bipyramidal one, with the distortion due to the close approach of the OH atom, i.e. 2.772(5) Å. A trigonal bipyramidal geometry is found in 2 where the oxygen atom, which forms significant O→Sn interactions of 2.498(4) and 2.550(4) Å for the two independent molecules, respectively, is in an apical position as is the iodine atom. The different strengths of the HO→Sn interactions are related to the Lewis acidities of the respective tin centers. Crystals of 1 are triclinic, space group P1, with a = 11.120(6) Å, b = 11.652(6) Å, c = 9.998(5) Å, α = 110.15(5)°, β = 106.39(4)°, γ = 87.74(6)°, V = 1164(1) Å3, and Z = 2. Crystals of 2 are triclinic, space group P1, with a = 12.631(4) Å, b = 13.887(1) Å, c = 12.252(4) Å, α = 95.91(2)°, β = 107.00(3)°, γ = 74.67(2)°, V = 1981(1) Å3, and Z = 2. The structures were refined to final R = 0.048 for 1 and R = 0.038 for 2. These compounds were characterized in solution by 1H, 13C, and 119Sn NMR spectroscopy. The existence of an intramolecular HO→Sn coordination in solution was assessed by 13C and 119Sn secondary isotope multiplet of partially labeled entities (SIMPLE-NMR) experiments. © 1994 American Chemical Society.