Four- and five-coordinate nickel(ii) complexes bearing new diphosphine-phosphonite and triphosphine-phosphite ligands: catalysts for N-alkylation of amines.

The reaction of Ph2PCH2OH with PhPCl2 and PCl3 in the presence of Et3N afforded new phosphonite compounds PhP(OCH2PPh2)21 and P(OCH2PPh2)32, respectively. The reaction between 1 and [NiCl2(DME)] in dichloromethane gave the five-coordinate complex [NiCl2(1-κ3 P,P,P)] 3. Conversely, 1 reacts with [NiCl2(DME)] in the presence of NH4PF6 in dichloromethane to yield the four coordinate ionic complex [NiCl(1-κ3 P,P,P)][PF6] 4. The reactions between 1, [NiCl2(DME)] and KPF6 in the presence of RNC (R = Xylyl, t Bu and iPr) in dichloromethane yielded the five coordinate monocationic [NiCl(1-κ3 P,P,P)(RNC)][PF6] (R = Xylyl) and dicationic [Ni(1-κ3 P,P,P)(RNC)2][PF6]2 (R = t Bu and iPr) complexes, respectively. The analogous reaction of 2 with [NiCl2(DME)] in the presence of KPF6 gave complex [NiCl(2-κ4 P,P,P,P)][PF6], 8. The structures of all complexes were determined by single crystal X-ray diffraction studies and supported by spectroscopic methods. To demonstrate their catalytic application, N-alkylation reactions between primary aryl amines, benzyl and 4-methoxy benzyl alcohols were found to proceed smoothly in the presence of 2.5 mol% of complexes bearing ligand 1 and <0.5 mmol of KOBu t in toluene at 140 °C. The C-N coupled products were formed in very good yields. Its substrate scope includes sterically encumbered, heterocyclic amines and aliphatic alcohol.