[(dcpp)Ni(η2-Arene)] Precursors: Synthesis, Reactivity, and Catalytic Application to the Suzuki-Miyaura Reaction

The complexes (Cy2PC3H6PCy2)Ni(eta(2)-arene) (arene = toluene (3), naphthalene (4)) have been synthesized and studied in detail. Displacement reactions of the toluene ligand afford the complexes (Cy2PC3H6PCy2)Ni(eta(2)-styrene) (5), (Cy2PC3H6PCy2)Ni (PhCN) (6), (Cy2PC3H6PCy2)Ni (CO)(2) (7), (Cy2PC3H6PCy2)Ni-(PPh3) (8), (Cy2PC3H6PCy2)Ni(PCy3) (9), {(Cy2PC3H6PCy2)Ni}(2)(mu-H)(2) (10), (Cy2PC3H6PCy2)Ni(eta(2)-CO2) (II), and [ (Cy2PC3H6PCy2)Ni](2) (mu, eta(2)-1,5-COD) (12). The relative rates of ArCl oxidative addition at Ni complexes 3, 4, 6, 8, and 12 have been evaluated experimentally, and the mechanism has been calculated by DFT. Complexes 3 and 4 are efficient catalysts for the Suzuki-Miyaura reaction between chloroarenes and Ar'B(OH)(2).