Preparation and infrared and 13C, 17O, and 119Sn NMR spectra of some substituted di- and tri(1-butyl)tin phenoxyacetates and phenylthioacetates

Abstract

The paper describes preparation and basic physical and chemical properties of a group of substituted di- and tri(1-butyl)tin(IV) phenoxyacetates and phenylthioacetates of the general formula (RxC6H5-xECH2CO2)nSn(1-C4H9)4-n, where R = H, 2-Cl, 4-Cl, 2-CH3, and 2-OCH3, E means oxygen or sulphur atoms, n = 1 or 2, and x = 1 or 2. From IR spectral data, 13C, 17O, and 119Sn NMR spectra, and from other physico-chemical methods, conclusions are drawn about structure of the compounds in solid state and in solutions of coordinating (hexamethylphosphoric triamide) and non-coordinating solvents (chloroform, carbon tetrachloride, carbon disulphide, benzene). In solid state the tri(1-butyl)tin(IV) compounds form polymeric chains with bidentate bridge carboxylic groups. In non-coordinating solvents these compounds are present as isolated pseudotetrahedral molecules, whereas in hexamethylphosphoric triamide they form complexes with one solvent molecule, the central tin atom exhibiting the trans-trigonally bipyramidal coordination. The di(1-butyl)tin(IV) compounds form, both in solid state and in non-coordinating solvents, monomeric particles containing bidentate chelate carboxylic groups. In hexamethylphosphoric triamide they form complexes with octahedral coordination around the tin atom containing monodentate carboxylic groups and the butyl groups are trans position. In none of the cases studied evidence was obtained for interaction of the oxygen or sulphur atoms of C6H5ECH2 group with the tin atom.

Tri-n-butyltin carboxylate derivatives of para-substituted phenyl-ethanoic acids: synthesis, characterization and X-ray structure determination

“…Such new bands are visible only in the solid state IR and are typical of pentacoordination at tin due to interaction with carbonyl groups; this is also confirmed by the Dt difference between the frequencies of asymmetrical and symmetrical stretching vibrations of the carboxyl moiety (186 and 210 cm À1 for III and VI, respectively). These values are close to those reported [15] for tin in the ionic form, and support the hypothesis of a structure involving bridged carboxylate groups located between planar SnR 3 groups with pentacoordinated tin, having a trigonal bipyramidal geometry, as formerly depicted in Chart 2.…”

Triorganotin 4-isopropylbenzoates as model transesterification catalysts for triorganotin carboxylates grafted to cross-linked polystyrene

“…1b and c), these bands being related to a carbonyl moiety free from any interaction with the metal atom [27], therefore evidencing tetracoordinated tin in 3 and 4 in the bulk. This behaviour, well established for analogue non-polymeric compounds bearing the triphenyltin carboxylate moiety, is uncommon for tributyltin derivatives.…”

Synthesis, characterization, and biological studies of tri‐ and diorganotin(IV) complexes with 2′,4′‐difluoro‐4‐hydroxy‐[1,1′]‐biphenyle‐3‐carbolic acid: Crystal structure of [(CH3)3Sn(C13H7O3F2)]

“…analogues as model compounds [29,30]. The positions of the phenyl carbon signals remains almost unchanged in the complexes as compared with those in the ligand acid.…”