Nucleophilicity of Ligated S22-Ions. Conversion of Organic Chlorides into Organosulfur Compounds incis-[(MCp*)2(μ-CH2)2(μ-S2R)]+(M = Rh, Ir)

The chemically active rhodium complex cis- [(RhCp*) 2 (μ-CH 2 ) 2 (μ-SS)], 1, activated all C−Cl bonds of polychlorinated organic compounds, namely, C 6 H 5 CCl 3 and p -ClC 6 H 4 CCl 3 (except ring chlorine), and formed compounds cis- [(RhCp*) 2 (μ-CH 2 ) 2 (μ-S 2 C-C 6 H 5 )][BPh 4 ], 6, and cis- [(RhCp*) 2 (μ-CH 2 ) 2 (μ-S 2 C-C 6 H 4 -Cl- p )][BPh 4 ], 7, after treatment with NaBPh 4 . Similarly, the iridium complex cis- [(IrCp*) 2 (μ-CH 2 ) 2 (μ-SS)], 2, activated C−Cl bonds of p -ClC 6 H 4 -CCl 3 (except ring chlorine) and formed the compound cis- [(IrCp*) 2 (μ-CH 2 ) 2 (μ-S 2 C-C 6 H 4 -Cl- p )][BPh 4 ], 5 . Compound 6 is analogous to cis- [(IrCp*) 2 (μ-CH 2 ) 2 (μ-S 2 C−C 6 H 5 )][BPh 4 ], 3 (obtained by reaction of 2 with C 6 H 5 CHCl 2 or C 6 H 5 CCl 3 ); however, reaction with C 6 H 5 CH 2 Cl formed the S-benzylated product cis -[(IrCp*) 2 (μ-CH 2 ) 2 (μ-SS-CH 2 -C 6 H 5 )][BPh 4 ], 4 . Interestingly, compound 2 activated all the C−Cl bonds of CCl 4 in methanol and formed the products cis -[(IrCp*) 2 (μ-CH 2 ) 2 (μ-S 2 CH)][BPh 4 ], 8, and [Ir 4 S 4 (Cp*) 4 (μ-CH 2 ) 4 ] [BPh 4 ] 2, 9 . The unique reactivity of the bridged S 2 -dimer is that activation of C−Cl bonds occurs at S-donor atoms and not at the usual metal centers.