Intramolecular Chalcogen−Tin Interactions in ( o -MeE-C 6 H 4 )CH 2 SnPh 3 - n Cl n (E = S, O; n = 0, 1, 2), Characterized by X-ray Diffraction and 119 Sn Solution and Solid-State NMR
2007; American Chemical Society; Volume: 46; Issue: 4 Linguagem: Inglês
10.1021/ic061811s
ISSN1520-510X
AutoresT. Munguia, Marcela López‐Cardoso, Francisco Cervantes‐Lee, Keith H. Pannell,
Tópico(s)Organometallic Complex Synthesis and Catalysis
ResumoOrganotin(IV) compounds of the type (o-MeE-C6H4)CH2SnPh3-nCln were synthesized, E = O, n = 0 (1), n = 1 (2), n = 2 (3) and E = S, n = 0 (4), n = 1 (5), n = 2 (6). The complexes exhibit significant trigonal bipyramidal pentacoordination at tin as a consequence of intramolecular Sn−O (1−3) and Sn−S (4−6) interactions upon substitution of the phenyl groups by chloro groups. The intramolecular Sn−O distances in 1, 2, and 3 are 83%, 75%, and 79% of the sum of the van der Waals radii. The equivalent Sn−S values for 4, 5, and 6 are 90%, 73%, and 71%, respectively. The geometry of compound 3 is complicated by intermolecular dimerization via bridging chlorines creating a distorted octahedral geometry at tin. The related dichloro sulfur compound 6 also exhibits an intermolecular association in the form of Sn−Cl−H hydrogen bonding leading to a polymeric structure in the solid state. CPMAS 119Sn NMR spectroscopy suggests that the intramolecular Sn−E interactions persist in solution and also facilitated the discovery of a new crystalline form of 4, 4', that contains a Sn−S distance which is 95% the sum of the van der Waals radii.
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