A Straightforward Synthesis of N ‐Functionalized β‐Diimines

Reaction of Schwartz’s reagent [Cp 2 ZrHCl] n ( 1 ) (one or two equivalents) with gem ‐dinitrile compounds of the type X(CN) 2 [X = CMe 2 , CBenz 2 , P(N iPr 2 ) 2 ] gives the corresponding mono‐ and di‐ N ‐zirconated imino complexes selectively. Substitution reactions of the zirconocene metal fragment with electrophiles such as, for example, chlorophosphanes of the type R 2 PCl, acid chlorides RC(O)Cl or the iminium salt [CH 2 NMe 2 ]Cl allowed the preparation of a large variety of stable N ‐functionalized mono‐ and β‐diimine derivatives. The nature of the X group is of particular importance for the success of the substitution reaction step. The X‐ray crystal structures obtained for the N ‐functionalized gem ‐aldimino‐nitrile compounds 9 , 10b , the N ‐phosphorylated β‐diimine 32 , and the gem ‐formyl nitrile derivative 12b are presented. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)