Abstract
AbstractThe reactivity of the reduced ZrIIICo0 heterobimetallic complex [(thf)Zr(MesNPiPr2)3CoN2] (1a) towards O–H, S–H, S–S, and O–O bonds has been investigated. Complex 1a reacts readily with PhOH, EtOH, and H2O to generate the one‐electron‐oxidized complexes [(RO)Zr(MesNPiPr2)3CoN2] [R = Et (2), Ph (3), H (4)]. In contrast, PhSH and PhS–SPh react by means of overall two‐electron processes to form [(η2‐MesNPiPr2)Zr(μ‐SPh)(MesNPiPr2)2Co(SPh)] (5a). Addition of stoichiometric diethyl peroxide to 1a generates 2, but further equivalents lead to the two‐electron oxidized product [(EtO)Zr(MesNPiPr2)3Co(OEt)] (6). More sterically hindered peroxides such as dicumyl peroxide or di‐tert‐butyl peroxide do not react with 1a under ambient conditions, but upon photolysis, di‐tert‐butyl peroxide reacts with 1a to form [(tBuO)Zr(MesNPiPr2)3CoN2] (7). These results imply that an inner‐sphere electron‐transfer process is occurring at the Zr site of 1a upon treatment with these chalcogen‐based substrates, and a dissociative electron‐transfer mechanism is proposed.
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.
