Synthesis of Cationic Ruthenium Thioketene Complexes through Intramolecular 1,2-Elimination [1]

Abstract

Halfsandwich thiocarboxylate complexes [CpRu(PR3)2(SC(O)CH2R′)] ((PR3)2 = (PPh3)2, Ph2PCH2PPh2 (dppm), Ph2PC2H4PPh2 (dppe); R′ = C6H5, 4-C6H4Me, 4-C6H4OMe, 4-C6H4Cl) are obtained from the corresponding thiolate complexes [CpRu(PR3)2SH] and acyl chlorides. The structure of [CpRu(dppm)(SC(O)CH2Ph)] was determined: monoclinic space group P21/c (No. 14), a = 9.229(2), b = 16.680(3), c = 21.447(5) Å, β = 90.751(12)°, Z = 4. Reaction of the thiocarboxylate complexes with the anhydrides of either trifluoro-acetic acid or trifluoromethanesulfonic acid gives thioketene complexes [CpRu(dppm) (η2-S=C=CHR′)]PF6.The structure of [CpRu(dppm)η-S= C = CHPh)]PF6 was determined: monoclinic space group P21/c (No. 14), a = 13.814(5), b = 15.338(2), c = 17.057(7) Å, β = 93.74(2)°, Z = 4