Tris phosphine, reaction with adducts

To date, however, only few reactions between phosphine and a non-metal halide, in which a chemical bond is formed between phosphorus and a non-metal by HCl condensation, are known. To these, apart from the above-mentioned reactions, belongs also the reaction with CF3SCI which, depending upon the chosen proportions of the reactants, in a sealed tube at -95 °C leads to the formation of (CF3S)2PH or (CF3S)3P Both compounds are not very stable thermally and decompose at 40-50 °C. Tris(trifluoromethylthio)-phosphine forms an unstable adduct with chlorine, which decomposes at 0 °C to give a mixture of PCI3, bis(trifluoromethyl)-disulphide and trifluoromethyl-sulphenyl chloride. 

Ring strain makes trimethylsilylcyclopropenes susceptible to attack by Ar3P such that further reaction with aldehyde is realized. A Brook-type rearrangement drives the reaction to completion by expulsion of the ArsP from the adducts. In practice, tris(2,4,6-trimethoxy-phenyl)phosphine is used instead of Ph3P (much better yields). ... 

Hydrazinum salts, reaction with MA, 84 Hydridodinitrogen tris-(triphenyl phosphine)co-balt, MA complex, 258 Hydrocarbons, C4 catalysts for oxidation, 37-40 oxidation mechanism, 33-37 Hydroformylation dialkyl fumarates, 45 dialkyl maleates, 45 Hydrogenation MA derivatives, 41-43 MA double bond, 41-42 Hydrogen cyanide, MA ester adducts, 229 Hydrogen halides addition to fumaric acid, 56 addition to maleic acid, 56 Hydrogen peroxide, 488 Hydrogen sulfide bismaleimide reaction, 514 MA reaction, 48, 49... 

Species such as XXV, XXVI, or XXVII readily form coordination complexes when treated with AuCl, H20So(C0)j q, Idn(CO)3(r -C5Hj), Fe(C0)3(PhCH=CHC(0)CH3>, or [RhCl(CO)2]2 ( ) Tw results are of special interest. First, the skeletal nitrogen atoms in XXV-XXVII do not participate in the coordination process. Presumably, they are effectively shielded by the aryloxy units and are of low basicity. Second, coordinatlve crosslinking can occur when two phosphine residues bind to one metal atom. Ligand-exchange reactions were detected for the rhodium-bound species. The tri-osmium cluster adducts of XXV, XXVI, and XXVII are catalysts for the isomerization of 1-hexane to 2-hexene. 

The radical reductive cyclisation of diesters to acyloins (see also Section 5.9.1, p. 628) is an important method of synthesis for ring sizes from four-membered upwards. The example selected here is 2-hydroxy-3-methylcyclopent-2-enone ( corylone ) (29) (Expt 7.10), which is an important perfumery and flavouring material.53 In the first step (i), methyl acrylate is converted into its dimer with tris(cyclohexyl)phosphine in pyridine solution.5b Step (ii) is the protection of the double bond by conversion into the dimethylamino adduct. The acyloin reaction is step (iii), and the product is trapped as its bis(trimethylsilyl)ether. Finally, in step (iv), the protecting dimethylamino and trimethylsilyl groups are removed by passage down a column of silica gel. 

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