Abstract
A novel ambiguous reactivity of Li/Cl phosphinidenoid complexes under redox conditions is described. The outcome of the reaction with hexafluoroacetone is highly dependent on the P-substituent as fluoride substitution occurred in the case of R = CPh3 and C5Me5via a radical pathway, whereas for R = CH(SiMe3)2 a complex having a novel 1,2-diol-type P-ligand was obtained via a closed-shell pathway. DFT calculations reveal a new SET pathway starting with a noncovalent π-hole complex between the phosphinidenoid anion and hexafluoroacetone followed by an elimination of LiF. The second, closed-shell reaction course is strongly influenced by a noncovalent OSi interaction established after the initial nucleophilic attack.
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.
