3,3-Bis(halomethylstannyl)propyl ethyl sulfoxides. The nature of intramolecular coordination in the crystals and in solution

Kamal Swami, John P. Hutchinson, Henry G. Kuivila, Jon A Zubieta

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Abstract

The preparations of 3,3-bis(chlorodimethylstannyl)propyl ethyl sulfoxide, (Me 2ClSn) 2CHCH 2CH 2S(O)Et, and of 3,3-bis(dichloromethylstannyl)propyl ethyl sulfoxide, (MeCl 2Sn) 2CHCH 2CH 2S(O)Et, are described. Structures of these compounds and of their bromo analogues have been determined by single-crystal X-ray diffraction. (Me 2ClSn) 2CHCH 2CH 2S(O)Et, 1, crystallizes in the triclinic space group P1 with a = 7.002 (3) Å, b = 9.383 (5) Å, c = 13.771 (7) Å, α = 104.35 (4)°, β = 98.67 (4)°, γ = 90.37 (4)°, V = 865.7 (7) Å 3, and D calcd = 1.867 g cm -3 for Z = 2. Full-matrix best-squares refinement of positional and anisotropic temperature parameter converged at a conventional residual of 0.068 for 1306 independent reflections. (MeCl 2Sn) 2CHCH 2CH 2S(O)Et, 2, crystallizes in the triclinic space group P1 with a = 9.099 (3) Å, b = 9.477 (3) Å, c = 10.476 (4) Å, α = 113.34 (2)°, β = 99.68 (2)°, γ = 91.87 (2)°, V = 812.7 (7) Å 3, and D calcd = 2.155 g cm -3 for Z = 2; R = 0.032 for 1842 reflections. (MeBr 2Sn) 2CHCH 2CH 2S(O)Et, 3, crystallizes in the space group P1 with a = 7.074 (2) Å, b = 9.325 (3) Å, c = 14.070 (6) Å, α = 77.45 (2)°, β = 81.03 (3)°, γ = 88.23 (2)°, V = 894.7 (7) Å 3, and D calcd = 2.136 g cm -3 for Z = 2; R = 0.078 for 1739 reflections. (MeBr 2Sn) 2CHCH 2CH 2S(O)Et, 4, crystallizes in the monoclinic space group P2 1/n with a = 8.965 (3) Å, b = 17.887 (7) Å 3, c = 11.166 (4) Å, β = 102.29 (2)°, V = 1749.5 (6) Å 3, D calc = 2.677 g cm -3, and Z = 4; R = 0.076 for 1128 reflections. The structures of 1 and 3 consist of discrete binuclear units with nonequivalent Sn atoms bridged symmetrically by a carbon of the propyl ethyl sulfoxide group and unsymmetrically by one or two halide atoms, depending on the degree of halide substitution. On the other hand, 2 and 4 exhibit halide bridging between two adjacent binuclear units to produce a loosely associated bimolecular or tetranuclear unit. The propyl ethyl sulfoxide ligand is coordinated through the sulfoxide oxygen donor to one tin atom in all cases. IR, 1H NMR, 13C NMR, and 119Sn NMR studies, coupled with the structural results, suggest that the oxygen of the sulfoxide group undergoes rapid coordinative exchange between the two tin atoms in each compound in solution.

Original languageEnglish (US)
Pages (from-to)1687-1694
Number of pages8
JournalOrganometallics
Volume3
Issue number11
StatePublished - 1984
Externally publishedYes

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ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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