Chemistry - A European Journal p. 16453 - 16460 (2013)
Update date:2022-08-28
Topics:
Herbert, David E.
Lara, Nadia C.
Agapie, Theodor
The meta-terphenyl diphosphine, m-P2, 1, was utilized to support Ni centers in the oxidation states 0, I, and II. A series of complexes bearing different substituents or ligands at Ni was prepared to investigate the dependence of metal-arene interactions on oxidation state and substitution at the metal center. Complex (m-P2)Ni (2) shows strong Ni 0-arene interactions involving the central arene ring of the terphenyl ligand both in solution and the solid state. These interactions are significantly less pronounced in Ni0 complexes bearing L-type ligands (2-L: L=CH3CN, CO, Ph2CN2), NiIX complexes (3-X: X=Cl, BF4, N3, N3B(C 6F5)3), and [(m-P2)Ni IICl2] (4). Complex 2 reacts with substrates, such as diphenyldiazoalkane, sulfur ylides (Ph2Si£CH2), organoazides (RN3: R=para-C6H4OMe, para-C 6H4CF3, 1-adamantyl), and N2O with the locus of observed reactivity dependent on the nature of the substrate. These reactions led to isolation of an η1-diphenyldiazoalkane adduct (2-Ph2CN2), methylidene insertion into a Nii£P bond followed by rearrangement of a nickel-bound phosphorus ylide (5) to a benzylphosphine (6), Staudinger oxidation of the phosphine arms, and metal-mediated nitrene insertion into an arene Ci£H bond of 1, all derived from the same compound (2). Hydrogen-atom abstraction from a NiI-amide (9) and the resulting nitrene transfer supports the viability of Ni-imide intermediates in the reaction of 1 with 1-azido-arenes. Put a ring on it: The utilization of a meta-terphenyl diphosphine ligand leads to labile metal-arene interactions in Ni complexes in various oxidation states and coordination environments. When these complexes are treated with group-transfer reagents, such as diazoalkanes, sulfur ylides, or azides, various types of ligand-centered reactivity were observed, including methylidene insertion into a Pi£C bond and amination of an arene Ci£H bond. Copyright
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