75416-90-9Relevant academic research and scientific papers
Quasiphosphonium Intermediates. Part 3. Preparation, Structure, and Reactivity of Alkoxyphosphonium Halides in the Reaction of Neopentyl Diphenylphosphinite, Dineopentyl Phenylphosphinite, and Trineopentyl Phosphite with Halogenomethanes and the Effect of Phenoxy-substituenst on the ...
Hudson, Harry R.,Kow, Aloysius,Roberts, John C.
, p. 1363 - 1368 (2007/10/02)
The reactions of neopenthyl diphenylphosphinite with chloro-, bromo-, or iodo-methane and of dineopentyl phenylphosphphonite with bromo- or iodo-methane yield crystalline alkoxyphosphonium halides.In deuteriochloroform these intermediates decompose by a first-order process which involves rate-determining collapse of the phosphonium halide ion-pair with SN2-type fission of the alkyl-oxygen bond.Rates for chloride, bromide, and iodide are similar.In a more ionising medium (deuterioacetonitrile) dissociation leads to stabilisation of the intermediates and to deviation from first-order decomposition.Previously determined X-ray diffraction data for the bromides, together with relative rates of decomposition in deuteriochloroform for intermediates in the series Phn(RO)3-nP+MeX- (n = 0,1, or 2) suggest that the stability and reactivity of alkoxyphosphonium intermediates are determined largely by inductive rather than mesomeric effects of ligands.The presence of phenoxy-substituents on phosphorus may cause a tendency towards SN1-type fission of the alkyl-oxygen bond in certain circumstances.
Michaelis-Arbuzow Intermediates: X-Ray Crystal Structures of the Methyl Bromide Adducts of Neopentyl Diphenylphosphinite and Dineopentyl Phenylphosphonite
Hendrick, Kim,Hudson, Harry R.,Kow, Aloysius
, p. 226 - 227 (2007/10/02)
Single crystal X-ray structure determinations of the Michaelis-Arbuzov intermediates Ph2Me(ButCH2O)P+Br- and PhMe(ButCH2O)2P+Br- clearly demonstrate that these species are four-co-ordinate phosphonium salts.
