Isomerization phosphorus, influence

Phosphorus-containing ligands show manifold influences on oxidation states and isomerisms in complexes and the extent of associations (see Chap. 3). The directing influence of varying properties in phosphines and phosphites was experimentally investigated for allyl-Ni-ligand complexes, e.g. with respect to ... 

During alkylation by alkyl halides in the presence of bases, -(2-oxoalkyl) phosphorodithioic esters have been found to undergo rearrangements of the general types (72) -> (73). The overall outcome is influenced both by experimental conditions as well as by the nature of other alkoxy groups attached to phosphorus. Thus, Q,Q-dimethyl -(2-oxo-2-phenylethyl) phosphorodithioate undergoes thione-thiol isomerization (72) -> (73a) in addition to dithiophosphate to thiophosphate rearrangement, (72) -> (73b),... 

A detailed study of the desulphurization of the disulphides (301)(R,R = dialkoxy, or alkyl(alkoxy) ) by phosphorus(III) compounds, including (Mc2N)2P, Ph P, or acyclic or cyclic (based on catechol) phosphotriesters or ester amides) considered the role of phosphonium and phosphorane intermediates. The isomerization of (302) into (303), and the decomposition (desulphurization, deoxygenation, or dealkylation) into end products, are influenced by electronic and steric factors. 

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