Synthesis and structural characterization of organotin(IV) complexes formed with [o,o] donor atoms of carboxylic acids

• Published in: Journal of the Serbian Chemical Society Vol. 73; no. 2; pp. 179 - 187
• Main Authors: Hussain, Mukhtiar, Zaman, Muhammad, Hanif, Muhammad, Ali, Saqib, Danish, Muhammad
• Format: Journal Article
• Language: English
• Published: Serbian Chemical Society 2008
• Subjects: nmr and mass spectrometry; o-donor ligands; organotin(iv) complexes
• ISSN: 0352-5139; 1820-7421
• DOI: 10.2298/JSC0802179H

Organotin(IV) carboxylates of the general formula RnSnL4-n (where R = Me, n-Bu or Ph, and L = ?-phenyl-2,3-(methylenedioxy)cinnamate anion or 2-(2,3-dimethlylanilino)nicotinate anion) have been prepared. The mono-, di- and tri-organotin(IV) carboxylates were synthesized by the reaction of organotin(IV) oxides or hydroxides with a stoichiometric amount of the ligand acids at an elevated temperature in dry toluene. The composition of the synthesized organotin(IV) complexes, the bonding behavior of the donor groups and structural assignments were studied by elemental analysis, FT-IR, 1H-, 13C-NMR and mass spectrometry. The spectral data suggest that the ligand acts in a bidentate manner, coordinating through the oxygen atoms. These spectroscopic techniques revealed a distorted tetrahedral geometry in the solution state for the tri-organotins, while a mean coordination number between five to six for the diorganotin(IV) dicarboxylates. In the solid phase, the tri-organotins were essentially trigonal bipyramidal polymeric while the di-organotins were octa?hedral. However, mono-organotin tricarboxylates were predicted to exist in the octahedral state both in solution as well as in the solid phase. U radu su dobijeni organokalaj(IV)-karboksilati opste formule RnSnL4-n (gde je R = Me, n-Bu i Ph grupa, a L = ?-fenil-2,3-(metilendioksi)-cinamatni anjon i 2-(2,3?dimetilanilino)-nikotinatni anjon). Mono-, di-i tri-organokalaj(IV) karboksilati sintetisani su reakcijom organokalajnih oksida ili hidroksida sa stehiometrijskom kolicinom kiseline na povisenoj temperaturi u suvom toluenu. Sastav izolovanih organokalaj(IV)-kompleksa, ponasanje vezujucih donorskih grupa i strukturno oznacavanje ispitivani su elementalnom analizom, FT-IR, 1H-, 13C-NMR i masenom spektrometrijom. Spektralni podaci ukazuju na to da je ligand bidentantno vezan, koordinirajuci se preko kiseonikovih atoma. Ove spektroskopske tehnike potvrdile su distorgovanu tetraedarsku geometriju u rastvoru za tri-organokalaj, a koordinacioni broj izmedju pet i sest za di-organokalaj(IV)-dikarboksilate. U cvrstom stanju, tri-organokalajna jedinjenja su pretezno tri?gonalno-bipiramidalni polimeri, a di-organokalajna oktaedarska. Medjutim, za mono-organokalajne trikarboksilate predlozeno je da su oktaedarski, i u rastvoru i u cvrstoj fazi.