Insertion reaction of carbon dioxide into Sn-OR bond. Synthesis, structure and DFT calculations of di- and tetranuclear isopropylcarbonato tin(IV) complexes.
The reaction of carbon dioxide with the stannane nBu2Sn(OiPr)2 and distannoxane [nBu2(iPrO)Sn]2O leads to the selective insertion into one Sn-OiPr bond generating the corresponding nBu2Sn(OiPr)(OCO2(i)Pr) and nBu2(iPrO)SnOSn(OCO2(i)Pr)nBu2 species. Both compounds are characterised by multinuclear NMR, FT-IR and single-crystal X-ray crystallography. In the solid state, they adopt a dimeric arrangement with bridging isopropoxy and terminal isopropylcarbonato ligands. The X-ray crystal structure of the dinuclear stannane shows that the Sn2O2 ring and the two Sn-OCO2C fragments are nearby coplanar. The same holds for the ladder-type tetranuclear distannoxane. The dimeric structures are also evidenced by solution NMR in non-coordinating solvents. Interestingly, the assignment of the exo and endo tin resonances of the dimeric distannoxane is unambiguous using a labeled 13CO2 experiment. The stability of the dimeric association has been probed in the stannane series on the basis of DFT calculations.
Ballivet-Tkatchenko
Danielle
D
LSEO, UMR 5188 CNRS-Université de Bourgogne, UFR Sciences et Techniques, BP 47870, 21078, Dijon Cedex, France. ballivet@u-bourgogne.fr
Chermette
Henry
H
Plasseraud
Laurent
L
Walter
Olaf
O
D002245:Carbon Dioxide / Q000737:chemistry*; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009947:Organotin Compounds / Q000138:chemical synthesis / Q000737:chemistry; D012680:Sensitivity and Specificity; D013237:Stereoisomerism
D009947:Organotin Compounds; D002245:Carbon Dioxide