| Abstract |
The preparation of 1,4,7-(NH(2-C6H4F)SiMe2\(3)-1,4,7-triazacyclononane (H3N3.(F)\9\N-3) and 1,4,8-\N(H)PhSiMe2\(3)-1,4,8-triazacycloundecane (H3N3[11]N-3), and their sodium derivatives Na3N3.(F)[9]N-3(THF)(2) and Na3N3[11]N-3(THF)(2), is described. The reaction of [TiCl3(THF)(3)] with Na3N3.(F)[9]N-3(THF)(2) and Na3N3[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-IV 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 Delta and Lambda enantiomers of [Ti\N-3[11]N-3)]I have been identified in solution. (c) Wiley-VCH Verlag GmbH \& Co. KGaA, 69451 Weinheim, Germany, 2005). |
