The reactions of Ph2PCH2SR (R = Me, Ph) in toluene with the dicobalt complexes [Co2 (μ-R1CCR2(CO)6] (R1 = R2 = CO2Me and R1 = H, R2 = CO2Me) give the monosubstituted complexes [Co2(μ-R1CCR2)(CO)5PPh 2CH2SMe] 1 and [Co2(μ- R1CCR2(CO)5PPh2CH2SPh] 2. On heating 1 and 2 in toluene solution, loss of CO leads to the bridged species [Co2(μ-R1CCR2)(μ- PPh2CH2SMe)(CO)4] 3 and [Co2 (μ -R1CCR2)(μ-PPh2CH2SPh)(CO) 4] 4. This transformation is readily reversed by treatment of 3 and 4 with CO, showing the Co-S bond in these complexes to be relatively weak. Similar reactions of Ph2PCH2SR (R = Me, Ph) with [Co2Fe(μ3-S)(CO)9], however, give only the ligand bridged species [Co2Fe(μ3-S)(μ-Ph2PCH 2SR)(CO)7] (R = Me 5 and R = Ph 6). Treatment of 5 and 6 with CO causes cleavage of the Co-S bond but, in contrast to 3 and 4, the ligand bridged species readily reform when the CO purge ceases. The structures of 3a and 6 have been confirmed by single-crystal X-ray analysis.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry