Tin(IV), Monomethyltin(IV), and Dimethyltin(IV) Complexes with thiol sulfur and heterocyclic nitrogen donors: Molecular dynamics and structure by ¹¹⁹Sn mössbauer spectroscopy

Abstract

Abstract The molecular dynamics of the complexes Sn(SPyN) 4 ( 1 ), SnCl 2 (SPyN) 2 ( 2 ), MeSn(SPy) 3 ( 3 ), MeSnCl(SPyN) 2 ( 4 ), Me 2 Sn(TCy) 2 ( 5 ), Me 2 SnCl(TOx) ( 6 ), and Me 2 Sn(TUr) ( 7 ) [HSPy = 2‐mercaptopyridine; HSPyN = 2‐mercaptopyrimidine; HTCy = 2‐thiocytosine; HTOx = 8‐thioquinoline; H 2 TUr = 2‐thiouracil] has been investigated by variable temperature 119 Sn Mössbauer spectroscopy. The area under the resonant peaks has been determined as function of temperature, from which Debye temperatures and cut‐off frequencies, as well as recoil‐free fractions (Lamb Mössbauer factor) and mean square displacements of 119 Sn, have been calculated. By fingerprint procedures on the basis of literature data, monomeric structures are attributed to complexes ( 1 )–( 4 ) and ( 6 ), while ( 5 ) and ( 7 ) lie in the borderline monomersmonodimensional polymers. The results are discussed on the basis of known crystal and molecular structures. The nature of the environment of tin atoms has been simulated by point‐charge model calculations of nuclear quadrupole splitting parameters; molecular structures are proposed for complexes ( 5 )–( 7 ), where no X‐ray diffractometric data are available.