Oxygen-Atom Transfer from Nitrous Oxide to an Organonickel(II) Phosphine Complex. Syntheses and Reactions of New Nickel(II) Aryloxides and the Crystal Structure of [cyclic] (Me2PCH2CH2PMe2)Ni(O-o-C6H4CMe2CH2)

PtII and RhIII Hydrocarbyl Complexes Bearing Coordinated Oxygen Atom Delivery Reagents

“…The [32][33][34] Cundari and co-workers have performed DFT calculations on the Hillhouse Ni-alkyl system [(bpy)-Ni{cyclo-(CH 2 ) 4 }] (bpy = 2,2Ј-bipyridyl) to investigate the mechanism of the oxygen-atom insertion. [35] The reaction of [(bpy)Ni(cyclo-CH 2 ) 4 ] with N 2 O, which affords a cyclic Ni-alkoxido, was found to proceed through a nickel-oxido intermediate.…”

“…[28,29] Oxygen atom insertion into Pd-aryl bonds has been reported, [30,31] and Hillhouse and coworkers have reported examples of Ni-alkyl-to-Ni-alkoxido transformations using N 2 O. [32][33][34][35] Abu-Omar and Espenson reported that the reaction of methyltrioxorhenium (MTO) with oxidants generates methanol, [36] and recently, Periana, Goddard, and co-workers reported a proposed mechanism for this reaction that proceeds by oxidant coordination and subsequent methyl migration to the coordinated oxygen. [37,38] The reaction has also been extended to an analogous Re-aryl system, O 3 ReAr (Ar = mesityl, 2,6-xylyl), to produce the corresponding phenol, and a flavincatalyzed variant with MTO has been reported.…”

N2O Reduction by the μ4‐Sulfide‐Bridged Tetranuclear CuZ Cluster Active Site

“…[3] Reduction of N 2 O in homogenous systems normally requires transition metals, such as Ti, V, Ni, Zr, Ru, Hf, [4][5][6][7][8][9] as activation centers, where the required two electrons are either derived from the metal centers, which results in terminal [10,11] or bridged [4] metal-oxide products, or from the ligands through insertion of the oxygen atom into the metal-ligand bond. [5][6][7]12] To date, none of the reported metal/N 2 O complexes has been structurally determined crystallographically. The N 2 O unit in the [(NH 3 ) 5 Ru(N 2 O)] 2+ complex has been found from spectroscopy to coordinate to the ruthenium atom in a linear end-on mode by its terminal nitrogen atom.…”

The para-substituent effect and pH-dependence of the organometallic Baeyer–Villiger oxidation of rhenium–carbon bonds

“…For example, the insertion of oxygen into palladium-aryl and nickel-aryl bonds is already known. [31][32][33] This class is more promising for integrating the OM-BV oxy-functionalization with alkane C-H activation, since late transition metals are known for activating alkane C-H bonds in oxidizing conditions. 11,34,35 Therefore, we will focus on those systems in the future.…”