The synthesis of dimetallic thioalkyne complexes of cobalt and molybdenum

Article abstract of DOI:10.1016/0022-328X(92)80229-Q

Treatment of CCR'2OH)(CO)6> with an excess of RSH in the presence of HBF4*OEt2 affords CCR'2SR)(CO)6> (R' = H, R = Et, ⁿBu, ^tBu, Ph, Bz; R' = Me, R = Et), which undergo substitution with bis(diphenylphosphino)methane (dppm) to give CCR'2SR)(μ-dppm)(CO)4>.Similar treatment of CCH2OH)(CO)5Cp> and CCH2OH)(CO)4Cp2> with EtSH gives CCH2SEt)(CO)5Cp> and CCH2SEt)(CO)4Cp2>, respectively.Reaction of CCH2OH)(CO)6> with a small excess of RSH (R = Et or Ph), ca. two equivalents, affords , while reaction with only one equivalent of EtSH additionally gives an ether-bridged system containing two hexacarbonyldicobalt units, CCH2OCH2C<*>CCH2SEt)-Co2(CO)6>.Treatment of CCH2SEt)(CO)6> with half an equivalent of HBF4*OEt2 affords CCH2OCH2C<*>CCH2SEt)Co2(CO)6>.Attempted preparation of mixed thioether complexes results in a mixture of products, and a mechanism is proposed for thioether scrambling.The IR, NMR and mass spectra of the new compounds are reported and discussed.