The reactions of CpRu(PPh3)2SR with the electrophiles HBF4, [MeSSMe2]BF4 and MeSphth where R=CMe3, CHMe2, 4-C6H4Me and phth=phthalimide

Reaction of the ruthenium thiolato complexes CpRu(PPh3)2SR (1), where R=CMe3, CHMe2, 4-C6H4Me with HBF4 gave the corresponding thiol complex salts [CpRu(PPh3)2(HSR)]BF4 (2) in very good yields. Treatment of the thiolato complexes with [MeSSMe2]BF4 gave the methyl thioether complex salt [CpRu(PPh3)2SMe2]BF4 (3). Reactions of 1 with MeSphth, where phth=phthalimide, gave CpRu(PPh3)2(phth) (4) and the dimers (μ-SMe)(μ-SR)[CpRu(phth)]2 (5) for R=CMe3 and CHMe2, however, for R=4-C6H4Me the same reaction gave CpRu(PPh3)(phth)(MeSS-4-C6H4Me) (6) and (μ-SMe)(μ-S-4-C6H4Me)[CpRu(S-4-C6H4Me)]2 (7). The crystal structure for 7 was determined: space group P21/c, a=8.805(2), b=13.668(3), c=26.026(6) Å, α=90, β=108.86(2), γ=90°, V=2964.0(12) Å3 and Z=4.