Elsevier

Polyhedron

Volume 11, Issue 21, 1992, Pages 2747-2755
Polyhedron

Ring size control in diorganotin sulphides by intramolecular SnN coordination

https://doi.org/10.1016/S0277-5387(00)83631-1Get rights and content

Abstract

The synthesis of intramolecularly coordinated organotin sulphides, [(Me2N CH2CH2CH2)2SnS]n (1) and [Me2NCH2CH2CH2Sn(Ph)S]n (2), is described. Compounds 1 and 2 are dimers in chloroform solution (n = 2). Compound 1 forms a centrosymmetric dimer with a planar rectangular Sn2S2 four-membered ring in its centre. The tin atoms show a distorted trans-cis-cis octahedral coordination by 2C, 2N and 2S. The tin-nitrogen distances are 2.810(3) and 3.158(5) Å. Compound 1 can be regarded as a model substance for nucleophilic attack at penta-coordinate tin centres. Although the degree of intramolecular coordination of nitrogen to tin is temperature dependent, the four-membered Sn2Sn2 ring remains inert in solution. The existence of the asymmetric tin compound (Me2NCH2CH2CH2)2SnS2SnBut2 (1a) has been characterized in solution.

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    When the N2 centre, being a Lewis base, attacks the Lewis acidic Sn1 center over the face C1C13S1, the axial Sn1-S1ʹ bond gets elongated in comparison to the axial Sn1-S1 bond [Fig. 1(c)]. The complex 1 has an Sn2S2 ring with an Sn1-S1 distance of 2.4007 Å and Sn1-S1ʹ distance of 2.4761 Å, which are in close agreement with previous reports on [R2Sn(µ-S)]2 rings bearing N → Sn intramolecular coordination. [24] Also, these bond parameters are much closer to the four membered Sn2S2 ring (Sn-S, 2.4001, 2.4817 Å and Sn-S-Sn, 86.79°) of our previously reported tetranuclear double decker compopund [(RSn)4(µ-S)6] (R = 2-phenylazophenyl). [9]

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