Bifunctional Pincer-type Organometallics as Substrates for Organic Transformations and as Novel Building Blocks for Polymetallic Materials

The reactivity of the bifunctionalized ligand NC(Br)N-I 1 [IC6H2(CH2NMe2)2-3,5-Br-4] has been
studied as a versatile synthon for organic and/or organometallic synthesis. Chemoselective metalation (M
= Pd, Pt, Li) at the Caryl−I or Caryl−Br bonds was achieved by choosing the appropriate metal precursors.
In this way a series of PtII and PdII complexes were prepared that have a second functional group available
for further reactions. These PtII and PdII complexes were subjected to a wide range of organic and
organometallic reactions, revealing the remarkable stability of their M−C σ-bond and opening an easy
route for the synthesis of mono- and (hetero)bimetallic building blocks. The scope of the chemistry of such
building blocks shows that they are good candidates for use in the synthesis of dendrimers, bioorganometallic
systems, or polymetallic materials. The X-ray crystal structures of the most representative complexes
(2, 3a, 19, 20, and 24) are also reported.