Aryltin chlorides and hydrides: Preparation, detailed NMR studies and DFT calculations

• Novel aryltin chlorides and hydrides were synthesized.
• Detailed 1H, 13C, and 119Sn NMR studies were performed.
• Single crystal X-ray characterization of novel aryltin dichlorides and trichlorides were carried out.
• Experimental data including 119Sn and 13C NMR shifts, 119Sn–13C coupling constants and bond lengths are supplemented by DFT calculations.

A series of novel tin chlorides RnSnCl4−n and respective hydrides RnSnH4−n were synthesized displaying a range of substituted phenyl residues, as well as naphthyl moieties (R = Ph, o-tolyl, 2,4-xylyl, 2,6-xylyl, p-biphenyl, 1-naphthyl, 2-naphthyl). These compounds were characterized using 1H, 13C and 119Sn NMR spectroscopy. In addition, X-ray diffraction was employed to elucidate the molecular structure of all solid aryltin chlorides (8–10, 14, 15). In each case, the tin is in a distorted tetrahedral environment. All naphthyl containing derivatives exhibit displaced π–π stacking. DFT calculations were carried out to compare experimental NMR data with calculated 13C and 119Sn shifts, as well as 13C–119Sn coupling constants.

The graphical abstract depicts a hydrogen coupled 119Sn NMR of four phenyl substituted organostannanes (Ph4Sn, Ph3SnH, Ph2SnH2, PhSnH3). In accordance to the number of hydrogen atoms bonded to the tin the multiplicity of the signal increases.Figure optionsDownload as PowerPoint slide