Substituted Benzyl Tin Compounds, Synthesis, Structure And Quantum Chemical Study

On recent years, people found that benzyltin compounds possessabundant structure character,reactivity, high bioactivity and low toxicity.The different substituents and its place, amount on aromatic ring haveobvious influence on reactivity and crystal structure.In order to understandthe influence of substituents' electronic effect and steric effect, Ten neworganotin compounds were synthesized by using 2-Br-C₆H₅CH₂Br,2-CN-C₆H₅CH₂Cl, 2,4-2Cl-C₆H₅CH₂Cl, 3,4-2Cl-C₆H₅CH₂Cl as substratesand characterized by elemental analysis, IR, ¹H NMR spectra, and 3 singlecrystal structures of the typical organotin compounds were determined.The variations on structure and property were also discussed.(1) Syntheses of a series of tribenzyltin(Ⅳ) chlorides R₃SnX (R=2-Br-C₆H₅CH₂-, 2-(CN)-C₆H₅CH₂-, X=Br, Cl), dibenzyltin(Ⅳ) chloridesR₂SnCl₂ (R=2,4-(2Cl)-C₆H₅CH₂-, 3,4-(2Cl)-C₆H₅CH₂-), bis(trialkyl)tin(Ⅳ)oxides (R₃Sn)₂O (R= 2-Br-C₆H₅CH₂-, 2-(CN)-C₆H₅CH₂-), R₄Sn (R=2-(CN)-C₆H₅CH₂-) and five substituted benzyltin carboxylate.(2) Tetra(o-cyanobenzyl)tin was synthesized by reaction of o-cyanobenzylchloride with tin in the solvent toluene under refluxing. It's X-raycrystallography diffraction analyses shows a distorted tetrahedral geometryaround the tin atom. Weak interactions [Sn…N(1) 0.3570nm] among themolecule,π-πOverlapping andσ-πOverlapping between benzene ringwhich constructs the three dimensional network structure.(3) Tri(o-bromobenzyl)tin 3-indolylacrylate was synthesized by reaction oftri(o-bromobenzyl)tin oxide with 3-indoleacrylic acid in the solventbenzene. It's X-ray crystallography diffraction analyses shows a distortedtetrahedral geometry around the tin atom. Three intermolecular hydrogenbonding among the molecule, as well as weak interactions such as N…O,π-πOverlapping between benzene ring and indole ring,σ-πOverlappingamong benzene ring which constructs the three dimensional networkstructure.(4) The complex [(2-quinolinecarboxylate)₂di(o-cyanobenzyl)tin(Ⅳ)] wassynthesized by reaction of tri(o-cyanobenzyl)tin chloride with2-quinolinecarboxylic acid catalyzed by triethylamine. It's X-ray crystallography diffraction analyses shows a distorted octahedral geometryaround the tin atom. Four intermolecular hydrogen bonding among themolecule, as well asπ-πOverlapping among double linkage(C=O) andquinoline ring which constructs the two dimensional network structure.(5) The reaction of carboxylic acid with the organotin haloids in thepresent of potassium hydroxideorganic and bases triethylamine wassystematically studied.(6) The quantum chemistry calculation by means of G98W package andtaking Lan12dz basis set were performed on Tetra(o-cyanobenzyl)tin,[(2-quinolinecarboxylate)₂di(o-cyanobenzyl)tin(Ⅳ)] and Tri(o-bromobenz-yl)tin 3-indolylacrylate. The stabilities of the complexes, some frontiermolecular orbital energies and composition characteristics of somefrontier molecular orbitals were investigated.