Nickel and Platinum PCP Pincer Complexes Incorporating an Acyclic Diaminoalkyl Central Moiety Connecting Imidazole or Pyrazole Rings

This work explores avenues toward PCP pincer complexes with acyclic diaminocarbene central moieties that are suitable for ligand-assisted reactivity involving the carbene carbon. For this purpose, diphosphine chelating ligands 1 and 2, with bis­(imidazolyl)­methyl and bis­(pyrazolyl)­methyl backbones, respectively, were prepared in two high-yield synthetic steps. Nickel­(II) and platinum­(II) dihalide complexes 3 and 6, incorporating 1, were prepared and converted into PCP pincer ligands 5 and 7 upon deprotonation with KHMDS. Chelated nickel­(I) complex 4 was obtained as a byproduct to 3. Although the solid-state structures of 5 and 7 presented geometric strain at the diaminomethyl carbon, this moiety could not be converted into a diaminocarbene by proton or hydride abstraction. 7 could be converted into platinum­(IV) analog 8 by oxidation with PhICl2. Ligand 2 proved more versatile than 1, or less dependable in its behavior, generating P,N-chelating cobalt­(II) dibromide complex 9. Easily accessible ligands 1 and 2 provide a new and versatile PCP pincer platform.