Reactions of Tungsten Alkylidynes with Thionyl Chloride

The reaction of [W(⋮CR)(CO)2(η-C5H5)] (R = C6H3Me2-2,6) with thionyl chloride provides the metallacyclic alkylidene complex [W(CRSCRS)Cl3(η-C5H5)], while similar treatment of [W(⋮CR)(CO)2{HB(pz)3}] (pz = pyrazol-1-yl) provides the alkylidyne complex [W(⋮CR)Cl2{HB(pz)3}], which is also obtained from the reaction of [W(⋮CR)(CO)2{HB(pz)3}] with [Fe(η-C5H5)2]Cl. The crystal structures of [W(⋮CC6H2Me3-2,4,6)(CO)2{HB(pz)3}], [W(CRSCRS)Cl3(η-C5H5)], and [W(⋮CR)Cl2{HB(pz)3}](R = C6H3Me2-2,6) are reported.