Abstract
The reactions of (Cl)Rh(PR3)3 (R = Me, Et) with the anionic thiapentadienide reagent lithium 2,3-dimethyl-5-thiapentadienide have been investigated. Treatment of (Cl)Rh(PMe3)3 with lithium 2,3-dimethyl-5-thiapentadienide produces ((1,2,5-η)-2,3-dimethyl-5-thiapentadienyl)Rh(PMe3)3 (1), in which the thiapentadienyl ligand is σ-bonded to rhodium through the sulfur end of the chain and π-bonded through the carbon end (C1−C2 double bond). In solution at room temperature, 1 undergoes a rapid dynamic process involving release and recoordination of the thiapentadienyl double bond C1−C2, causing two of the phosphine ligands to become equivalent. The intermediate in which the double bond C1−C2 is released from the rhodium center can be “trapped” as a dioxygen adduct, ((5-η)-2,3-dimethyl-5-thiapentadienyl)Rh(PMe3)3(η2-O2) (2). When it is stirred at room temperature in tetrahydrofuran solution, 1 slowly rearranges to ((1,4,5-η)-2,3-dimethyl-5-thiapentadienyl)Rh(PMe3)3 (3), the thermodynamic isomer in which the thiap...
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
