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Cationic Indium Alkyl Complexes Incorporating Aminotroponiminate Ligands

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journal contribution
posted on 20.02.2002, 00:00 by Fabien Delpech, Ilia A. Guzei, Richard F. Jordan
The synthesis and structures of indium complexes incorporating the bidentate monoanionic ligand N,N-diisopropylaminotroponiminate (iPr2-ATI) are described. The reaction of InCl3 with Li[iPr2-ATI] yields (iPr2-ATI)InCl2 (3), which is converted to (iPr2-ATI)InMe2 (4) by reaction with MeLi; 4 is also formed by the reaction of InMe3 with (iPr2-ATI)H. The reaction of 4 with [Ph3C][B(C6F5)4] at 23 °C yields the diimine complex [{1,2-(NiPr)2-5-CPh3-cyclohepta-3,6-diene}InMe2][B(C6F5)4] (5) via addition of Ph3C+ to the C5 carbon of 4. Thermolysis of 5 (75 °C) yields [(iPr2-ATI)InMe][B(C6F5)4] (6) and Ph3CMe. 6 was isolated as the chlorobenzene solvate 6·PhCl. An X-ray diffraction study shows that there are two independent cations in the asymmetric unit of 6·PhCl. One cation (In(1)) is ion-paired with two B(C6F5)4- anions, while the second cation is complexed with two PhCl molecules and is disordered between two equally occupied positions (In(2) and In(3)). Dative In−ClPh bonding and PhCl/ATI π-stacking interactions contribute to the PhCl coordination in 6·PhCl. The reaction of 4 with B(C6F5)3 yields [(iPr2-ATI)InMe][MeB(C6F5)3] (7), which decomposes slowly at 23 °C by C6F5- transfer reactions. The reaction of 4 with [HNMe2Ph][B(C6F5)4] yields the labile amine adduct [(iPr2-ATI)In(Me)(NMe2Ph)][B(C6F5)4] (10).