Abstract
Oxidation of in situ generated Li/X phosphinidenoid complexes [(OC)5W{(Me3Si)2CHP(X)Li/12-crown-4}] (X = F (2), Cl (6)) with TEMPO at −78 °C led to the lithium halogenophosphinite complexes [(OC)5W{(Me3Si)2CHP(X)OLi/12-crown-4}] (4) via an unknown pathway possibly involving transient P-nitroxyl complex derivatives (3). Whereas 4a (X = F) could be isolated directly, 4b (X = Cl) underwent facile hydrolysis to give the lithium phosphonite complex [(OC)5W{(Me3Si)2CHP(OH)OLi/12-crown-4}] (7) as the final product; the structures of complexes 4a and 7 were firmly established by single-crystal X-ray analysis. DFT calculations on the assumed intermediate P-nitroxyl complexes 3a,b reveal a preference for homolytic N–O over P–O bond cleavage, as underlined by the small bond dissociation energies (in kcal/mol: 3a, P–O 53.2 and N–O 26.0; 3b, P–O 35.4 and N–O 20.8).
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.
