Intramolecular chalcogen-tin interactions in (o-MeE-C6H4)CH2SnPh3-nCln (E = S, O; n = 0, 1, 2), characterized by X-ray diffraction and 119Sn solution and solid-state NMR.
Organotin(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.
Munguia
Teresita
T
Department of Chemistry, University of Texas at El Paso, El Paso, TX 79968-0513, USA.
López-Cardoso
Marcela
M
Cervantes-Lee
Francisco
F
Pannell
Keith H
KH
D018011:Chalcogens / Q000737:chemistry*; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009947:Organotin Compounds / Q000138:chemical synthesis*; D010100:Oxygen / Q000737:chemistry; D012996:Solutions / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry; D014001:Tin / Q000737:chemistry; D014004:Tin Radioisotopes; D014961:X-Ray Diffraction
D018011:Chalcogens; D009947:Organotin Compounds; D012996:Solutions; D014004:Tin Radioisotopes; D013455:Sulfur; D014001:Tin; D010100:Oxygen