Hydrated and Solvated Tin(II) Ions in Solution and the Solid State, and a Coordination Chemistry Overview of the d¹⁰s² Metal Ions

Abstract

SynopsisThe coordination chemistry of tin(II) is strongly affected by the partially filled Sn(5s)-ligand(np) anti-bonding orbital causing structural distortions including a large void in the coordination sphere. The mean tin-ligand atom bond distance varies largely with type of ligand atom, even within the same coordination number. The actual coordination number and bond angles of tin(II) complexes seems to depend on tin-ligand bond character.

Structural, vibrational and electronic properties of SnMBO4 (M = Al, Ga): a predictive hybrid DFT study

“…Pb 2+ ), a rigid BO 3 trigonal planar unit, and a suitably sized M-cation forming edge-sharing octahedra that run parallel to the c-axis [2]. Since the radius of the Sn 2+ cation is similar to that of Pb 2+ [8], these two cations are expected to be readily exchanged in the structure, showing 5s 2 and 6s 2 LEP activities, respectively. Whereas Pb 2+ is stable [9], compounds with Sn 2+ are usually moderate reducing agents [10].…”

On solvated tin(iv) ions and the coordination chemistry of high-valent d10 metal ions

“…Structure of the dimethylsulfoxide solvated methyltin(IV) ion Tin(II) is slowly oxidized to tin(IV) and dmso is reduced to dimethylsulfide, characterized by its intense smell, in a dmso solution of tin(II) perchlorate. 3 After reducing the volume of the solution by evaporation and cooling in refrigerator crystals of pentakis(dmso)methyltin(IV) perchlorate [CH 3 Sn(OS(CH 3 ) 2 ) 5 ] (ClO 4 ) 3 , 1, of sufficient quality for a crystallographic study were obtained. The crystal structure of 1 shows that tin(IV) binds five dmso molecules, mean Sn-O bond distance 2.099 Å, and a methyl group at 2.113 Å in a slightly distorted octahedral fashion, with an overall mean Sn-O/C bond distance of 2.101 Å, Table 2.…”

“…The coordination chemistry of tin(II) and lead(II) is strongly affected by occupied anti-bonding orbitals causing large voids, so-called gaps, in their coordination spheres. [3][4][5][6] This is not the case for the tetravalent ions, but for neither tin(IV) nor lead(IV), no hydrate or solvate structures have previously been reported. We have made several attempts to prepare aqueous solutions of hydrated tin(IV) ions in strongly acidic solution, but it always resulted in precipitation of solid tin(IV) oxide, SnO 2 .…”

“…The preparation procedures of the studied tin(II) dmso and dmtf solutions are described in detail elsewhere. 3 These solutions were stored in closed glass vials at room temperature for 12 years. The volume of the dmso solution was reduced by evaporation under vacuum and pentakis(dmso)methyltin(IV) perchlorate, [CH 3 Sn(OS(CH 3 ) 2 ) 5 ](ClO 4 ) 3 , 1, precipitated after refrigeration.…”

“…The aim of this study was to explore the contents of dimethylsulfoxide (dmso) and N,N-dimethylthioformamide (dmtf ) solutions of tin(II) prepared for the study the coordination chemistry of tin(II). 3 They were stored for 12 years in closed vessels at room temperature and, when opened, the dmso solution had an intense and characteristic smell of dimethylsulfide, (CH 3 ) 2 S. This strongly indicated that at least part of the dmso had been reduced and that an oxidation product had formed. Similarly, in the dmtf solution, another oxidation product had formed, where tin(II) upon being oxidized to tin(IV) had reduced some of the dmtf.…”