Phenoxide ligand, formation

Various UV/Vis spectroscopic studies have been described by Reedijk and co-workers, aimed at identifying the proposed dicopper species with bridging methoxide and phenoxide ligands (compare 8) in the absence of neocuproine. Notion is made of two bands, appearing at 420 and 450cm which were attributed to the formation of /z-OMe and /z-phenoxo bridges, respectively. 

Using 1,4,8,11-tetraazacyclotetradecane, the structure of complex (800) (distorted trigonal planar Cu-Cu 6.739 A) was determined. Reactivity with 02 was investigated to demonstrate the formation of trans-l,2-peroxo species.585 As part of their work with copper(I) complexes with 02, the structure of a dicopper(I) complex ((801) distorted tetrahedral 7.04 A), supported by macrocyclic ligand environment, was reported by Comba and co-workers. Tolman and co-workers structurally characterized a three-coordinate copper(I)-phenoxide complex (802) (planar T-shaped) that models the reduced form of GO.587 The copper(I) analogue [Cu(L)][CF3-SO3]-0.43MeOI I (803) of a copper(II) complex (534) was also reported to demonstrate the role of ligand framework conformability in CV /Cu1 redox potentials.434 Wilson and co-workers... 

Homoleptic phenoxido complexes of the composition [Re(L)4] where L = 2,6-diisopropylphenoxide or 2,6-dimethylphenoxide have been prepared by the reaction of [ReCl4(THF)2] with the lithium salts of the ligands. The molecular geometry is square planar and the metal center is well protected from above and below the Re04 plane by the isopropyl groups and protects the complex from reactions with alkynes, whereas such a reaction and the formation of [Re(OC6H3-2,6-Me2)4(RC=CR)] adducts (R = Me, Eth, Ph) has been observed for the dimethyl derivative of the phenoxide. ... 

It has been shown that reaction of Mn30(02CPh)6(py)2(H20) with [NEt3H]2(biphenoxide) results in the formation of [Mn(III)(biphen)2-(biphenH)]2- (biphen = 2,2 -biphenoxide) (Fig. 5) (143). The complex is a rare example of five-coordinate Mn(III) without softer ligands such as thiolate or chloride. The monodentate biphen-Mn bond represents the first stable example of the Mn phenoxide couple. The monomer displays several intense absorption bands (Table VI). In DMSO (where the compound may be six coordinate), a band at 430 nm, very similar to that of the enzyme, is assigned to a phenoxide - Mn(III) charge transfer band. 

Aryl ethers. Pd-mediated C-O bond formation ameliorates the undesirable feature of the Ullmann method employing stoichiometric quantities of copper salts. Electron-deficient ArBr and electron-rich ArONa are suitable reaction partners. Electron-poor phosphine ligands improve the yields of the displacement reaction between aryl bromides and sodium phenoxides. 

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