Hypercoordinated Organotin(<scp>IV</scp>) Halides Containing 2‐(Me₂NCH₂)C₆H₄ Groups: {2‐(Me₂NCH₂)C₆H₄}₂SnX₂ (X = F, Cl, Br, I) and {2‐(Me₂NCH₂)C₆H₄}R₂SnX (R = Me, Ph; X = F, Cl, Br, I) and Their Solution Behaviour and Solid‐State, Hydrogen‐Bonding‐Based Supramolecular Architecture

Abstract

Abstract The hypercoordinated di‐ and triorganotin( IV ) chlorides [{2‐(Me 2 NCH 2 )C 6 H 4 } 2 SnCl 2 ] ( 1a ) and [{2‐(Me 2 NCH 2 )C 6 H 4 }R 2 SnCl] [R = Me ( 2a ), Ph ( 3a )] were prepared by treating SnCl 4 or R 2 SnCl 2 with [Li{2‐(Me 2 NCH 2 )C 6 H 4 }]. Halide‐exchange reactions between the organotin( IV ) chlorides and the appropriate potassium halides gave [{2‐(Me 2 NCH 2 )C 6 H 4 } 2 SnX 2 ] [X = F ( 1b ), I ( 1d )], [{2‐(Me 2 NCH 2 )C 6 H 4 }Me 2 SnX] [X = F ( 2b ), Br ( 2c ), I ( 2d )] and [{2‐(Me 2 NCH 2 )C 6 H 4 }Ph 2 SnX] [X = F ( 3b ), I ( 3d )]. Their solution behaviour was investigated by multinuclear ( 1 H, 13 C, 19 F and 119 Sn) NMR spectroscopy, including variable‐temperature studies. Single‐crystal X‐ray diffraction analyses revealed that the strong intramolecular coordination of the nitrogen atom from the pendant CH 2 NMe 2 group to tin induces chirality. The influence of the identity and the number of the halogen atoms and the organic substituents at tin is discussed in relation with the hydrogen‐bonding network, which results in different supramolecular architectures in the crystal. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2006)