One-step preparation, structural assignment, and X-ray study of 2,2-di-n-butyl- and 2,2-diphenyl-6-aza-1,3-dioxa-2-stannabenzocyclononen-4-ones derived from amino acids.
Twenty-four 2,2-di-n-butyl- and 2,2-diphenyl-6-aza-1,3-dioxa-2-stannabenzocyclononen-4-ones, each having a transannular N-->Sn bond, have been prepared by one-step reactions of alpha-amino acids (1 a-l), salicylaldehyde (2), and either di-n-butyltin(IV) oxide (3) or diphenyltin(IV) oxide (4). The new methodology constitutes an easy, highly efficient one-step synthesis of diorganotin(IV) derivatives, such as 5 a-l and 6 a-l, from iminic tridentate ligands without isolation of the Schiff bases. The structures of all the compounds have been established by a combination of (1)H, (13)C, (15)N, and (119)Sn NMR spectroscopy, IR spectroscopy, mass spectrometry, and elemental analysis. In all cases, the (119)Sn chemical shifts, as well as the (1)J((119)Sn,(13)C) coupling constants, are indicative of pentacoordinated tin atoms in solution. The structures of compounds 5 a, d, f, 6 a, b, b-racemic, c, d, f, g, and l have been established by single-crystal X-ray diffraction analyses. The tin atoms in 5 d, f, 6 a, b, b-racemic, c, d, g, and l each have a distorted trigonal-bipyramidal (TBP) geometry, with the oxygen atoms from the phenol and carboxylate moieties occupying the axial positions, and the imine nitrogen and phenyl or n-butyl substituents occupying the equatorial positions. Compounds 5 a and 6 f show distorted octahedral (DOC) geometries due to intermolecular coordination of the carbonyl oxygen to the tin atom, in a trans disposition to the N-->Sn bond, leading to trimeric 5 a and a polymeric structure for compound 6 f. Additionally, measurement of the one-bond coupling constants (1)J((119)Sn,(13)C) in diphenyltin(IV) complexes (6 a-l) and their correlation with the CSn-C bond angles has allowed the derivation of an equation that can be applied to assess the geometry around the tin atom for other diphenyltin(IV) compounds in solution.
Beltrán
Hiram I
HI
Departamento de Química, Centro de Investigación y de Estudios Avanzados, del Instituto Politécnico Nacional Apdo Postal 14-740, 07000 México, DF, México.
Zamudio-Rivera
Luis S
LS
Mancilla
Teresa
T
Santillan
Rosa
R
Farfán
Norberto
N
D000596:Amino Acids / Q000737:chemistry*; D001372:Aza Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D001713:Biphenyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D009947:Organotin Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013057:Spectrum Analysis / Q000379:methods
D000596:Amino Acids; D001372:Aza Compounds; D001713:Biphenyl Compounds; D007659:Ketones; D009947:Organotin Compounds