Oxygen aryloxides

Oxygen-Gontaining Organics. Neutral and anionic oxygen-containing organic molecules form complexes with thorium. Recent work has focused on alkoxides (72), aryloxides, and carboxylates however, complexes with alcohols, ethers, esters, ketones, aldehydes, ketoenolates, and carbamates are also well known. 

The low spin aryliron complexes Fe(Por)Ar behave differently than their alkyl counterparts toward oxygen. In chloroform the products of the reaction of Fe(Por)Ar with O2 are the iron(IV) alkyl Fe(Por)Ar] and Fe(Por)Cl, while in toluene the aryloxide complexes Fe(Por)OAr are formed with no direct evidence for the formation of arylperoxo intermediates."" The high spin iron(lll) alkynyl complexes which have more ionic character in the Fe—C bond do not react with oxygen, and the order of reactivity of organoiron(lll) complexes toward O2 is given by Fe(Por)(alkyl) > Fe(Por)(aryl) > Fe(Por)(C=CR). ... 

Metal-Oxygen Bond Lengths, M—O—C Angles, and Torsion Angles for Three-Coordinate Aluminum and Gallium Alkoxides and Aryloxides... 

Alkoxide or aryloxide anions are also reputed to be inactive in Sr I reactions. There is, however, one example of such a reaction at an sp carbon the nitro-derivative of 4-nitrocumyl reacts with phenoxide and 1-methyl-2-naphthoxide ions yielding the corresponding ethers (Kornblum et al., 1967). A similar reaction has been reported for halobenzenes in t-butyl alcohol upon stimulation by sodium amalgam (Rajan and Sridaran, 1977). This reaction could not, however, be reproduced (Rossi and Pierini, 1980) and other attempts to make phenoxide ions react at sp carbons have been equally unsuccessful (Ciminale et al, 1978 Rossi and Bunnett, 1973 Semmelhack and Bargar, 1980). It has been found, more recently, that phenoxide ions react with a series of aryl halides under electrochemical induction, but that the coupling occurs at the p- or o-phenolic carbon rather than at the phenolic oxygen (Alam et al, 1988 Amatore et al, 1988). This is... 

The mechanism of the thermal ROP of (Cl2PN)3 has been proposed to involve a cationic mechanism (see Scheme 8.2 in Section 8.1.2.2). The unique reaction sequence involving ROP followed by nucleophilic substitution with oxygen- or nitrogen-based nucleophiles (generally alkoxides, aryloxides or primary amines) permits a diverse range of polyorganophosphazenes to be... 

Alkoxide and aryloxide ions are not arylated on oxygen. Tertiary alkoxides do not react, thus making them appropriate bases for generation of nucleophiles, and primary and secondary alkoxides undergo a-hydrogen abstraction with aryl radicals normally making them unsuitable for use as bases e.g. isopro-poxide ion reacts with phenyl radicals to give benzene and acetone ketyl.58 The C-arylation of aryloxides is discussed in Section 2.2.3.1.4. 

The different products which are obtained due to hydroxybenzyl migration can be trapped by metal complexation. The thus formed trivalent, N403-encapsulating ligand adopts a pentagonal bipyramidal geometry at the ytterbium center with two aryloxide oxygens in the axial positions. 

The reaction product of ytterbium metal with benzophenone in a 1 1 molar ratio could be determined by an X-ray structure [278]. The benzophenone dianion unsymmetrically bridges the ytterbium atoms in the HMPA solvate [Yb(OCPh2)2(HMPA)2]2. The aryl oxygen forms a Yb-O bond with a typical terminal bond length (Table 18), but also donates to the other ytterbium. A Yb-C a-bond involving the a-C-atom (2.59(5) A) balances the charge at Yb (II). Reaction of the dianionic complex with four equivalents of phenol HOC6H3tBu2-2,6-Me-4 afforded the mononuclear aryloxide complex Yb(OAr)2(HMPA)2 (Sect. 4.2) [72],... 

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