850513-39-2Relevant articles and documents
The course of oxidative addition reactions of haloalkynes and haloalkenes to dimethyl- and dialkynylaurate(I) anions [RAuR]-
Schuster, Oliver,Schmidbaur, Hubert
, p. 3769 - 3775 (2008/10/09)
The reactions of halo-alkynes Cl-C{triple bond, long}CH, C-lC{triple bond, long}C-Cl or PhC{triple bond, long}C-I with solutions of Li+[MeAuMe]- in diethylether containing Ph3P do not give the expected oxidative addition products Me2(RC{triple bond, long}C)Au(PPh3) with R = H, Cl, Ph. A mixture of other complexes is obtained instead which are generated in secondary reactions involving reductive elimination of ethane and/or dialkyne. However, addition of the halo-alkene H(Cl)C{double bond, long}CCl2 to the same substrate solution affords trans-Me2[trans-H(Cl)C{double bond, long}C(Cl)]Au(PPh3) in good yield. Its molecular structure with pseudo-Cs symmetry has been determined by the solution NMR spectra and a single-crystal X-ray diffraction study. The reaction of methyl iodide with solutions of Li+[RC{triple bond, long}CAuC{triple bond, long}CR]- in diethylether containing PPh3 give the quaternary salts Ph3PMe+ [RC{triple bond, long}CAuC{triple bond, long}CR]- as the main products and only small amounts of cis-Me2(RC{triple bond, long}C)Au(PPh3) complexes probably formed in a series of oxidative addition, reductive elimination, and substitution reactions. The structure of Ph3PMe+ [PhC{triple bond, long}CAuC{triple bond, long}CPh]- has been determined.
