Reactions of amino-imino-boranes with transition metal halides and substituted transition metal halides

The aminoiminoborane tmp-B equivalent to NCMe3 (1) adds to TiBr4 or ZrCl4 i n a 1:1 ratio while PdCl2 adds 1 in a 1:2 ratio. In these new compounds the NBN unit is almost linear and the configuration corresponds to an allene. On the other hand 1 and Ti(OR)(4) compounds and Ti(NMe2)(4) give N metallat ed diaminoboranes tmp-B(X)-NCMC3EX3 (X = OR, NMe2). Mixed compounds Ti(OR)( 3-n)X-n lead to diaminoboranes with BOR groups while the TiCl bond inserts into the B equivalent toN bond of 1 to produce tmp-BNMe2-NCMe3TiCl3. Hydrol ysis of this compound leads to a spirocyclic dititanoxane with a short line ar 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 when 1 is all owed to react with TiCl4, NTbCl5, TaCl5 and PdCl2. The palladium compound 1 6 is dimeric, and dimerization occurs via Pd-Cl bridges. The aminoiminoborane tmp-B=NC6H3-2,6-iPr(2) reacts with the titanium compou nds in the same manner as 1, however without formation of spirocycles.