Abstract
A series of three neutral, hexacoordinate tin(IV) complexes were synthesized by the reaction of 4,4'‐dimethyl‐2,2'‐bipyridine (DMB) with SnX4, X = Cl, Br, and I, as starting materials. The complexes (DMB)SnX4 were characterized in solution by 1H, 13C, and 119Sn NMR spectroscopy, and in the solid‐state by 119Sn MAS NMR spectroscopy. In addition, single‐crystal X‐ray diffraction and elemental analysis were used to confirm the molecular structures. In these complexes, the tin atom adopts a distorted octahedral arrangement and the DMB acts as a bidentate N,N'‐chelate ligand. Computational DFT methods were also employed to gain more insight into the nature of the bonding in these complexes, including the hypothetical complexes (DMB)SnX4 (X = F, At). Additionally, the validity and reliability of the 119Sn NMR chemical shifts were examined. The calculated values were compared with the experimental signals and the effects of structure and solvent are discussed. Finally, all of the complexes (DMB)SnX4 were successfully tested for the ring‐opening polymerization (ROP) of bulk ε‐caprolactone under non‐dried and aerobic conditions as precatalyst.
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