Titanium Triamidotriamine Compounds: Syntheses, Structures and Redox Properties

The preparation of 1,4,7-(NH(2-C6H4F)SiMe2)3-1,4,7-triazacyclononane (H 3 N 3 - F [9]N 3 ) and 1,4,8-(N(H)PhSiMe 2 } 3 -1,4,8-triazacycloundecane (H 3 N 3 [11]N 3 ), and their sodium derivatives Na 3 N 3 - F [9]N 3 (THF) 2 and Na 3 N 3 [11]N 3 (THF) 2 , is described. The reaction of [TiCl 3 (THF) 3 ) with Na 3 N 3 - F [9]-N 3 (THF) 2 and Na 3 N 3 [11]N 3 (THF) 2 leads to [Ti(N 3 - F [9]N 3 )] and [Ti{N 3 [11]N 3 }]. The titanium complexes react readily with I 2 to give the Ti I V derivatives [Ti{N 3 - F [9]N 3 }]I and [Ti{N 3 [11]N 3 }]I. All titanium compounds display distorted trigonal prismatic geometries where the metal is coordinated to the six nitrogen donors. Fluxional processes that convert the conformations of the five- and six-membered metallacycles and the A and A enantiomers of [Ti{N 3 [11]N 3 }]I have been identified in solution.