Reactions of Amino-imino-boranes with Transition Metal Halides and Substituted Transition Metal Halides
Barbara B¨ock, Heinrich N¨oth, and Ulrich Wietelmann
Department of Chemistry, University of Munich,Butenandtstr. 5 - 13, D-81 377 M¨unchen, Germany
Reprint requests to Prof. Dr. H. N¨oth. E-mail H.Noeth@lrz.uni-muenchen.de Dedicated to Professor Dr. H. P. Fritz
Z. Naturforsch.56 b,659–670 (2001); received May 3, 2001
Adducts of Aminoimino Boranes, Metallated Diaminoboranes, Titanium
The aminoiminoborane tmp-BNCMe3(1) adds to TiBr4or ZrCl4in a 1:1 ratio while PdCl2
adds1in a 1:2 ratio. In these new compounds the NBN unit is almost linear and the configuration corresponds to an allene. On the other hand1and Ti(OR)4compounds and Ti(NMe2)4give N metallated diaminoboranes tmp-B(X)-NCMe3EX3 (X = OR, NMe2). Mixed compounds Ti(OR)3 nXnlead to diaminoboranes with BOR groups while the TiCl bond inserts into the BN bond of1to produce tmp-BNMe2-NCMe3TiCl3. Hydrolysis of this compound leads to a spirocyclic dititanoxane with a short linear Ti-O-Ti bond and pentacoordinated Ti centers carrying two Cl atoms each. Spirocycles with a BN2E (E = Ti, Nb, Ta, Pd) unit are formed when1is allowed to react with TiCl4, NbCl5, TaCl5and PdCl2. The palladium compound16is dimeric, and dimerization occurs via Pd-Cl bridges.
The aminoiminoborane tmp-B=NC6H3-2,6-iPr2reacts with the titanium compounds in the same manner as1, however without formation of spirocycles.
