A novel cobalt system featuring a Co–P moiety has been synthesized to study its metal–ligand cooperativity.A reversible conversion of a phosphide group to a P–P bond found in a dimeric cobalt(Ⅰ)complex involves el...A novel cobalt system featuring a Co–P moiety has been synthesized to study its metal–ligand cooperativity.A reversible conversion of a phosphide group to a P–P bond found in a dimeric cobalt(Ⅰ)complex involves electron transfer between Co and P,in which a single electron transfer is successfully coupled with a redox change in each cobalt ion.Upon coordination of aπ-acidic ligand such as acetonitrile and isocyanide at the cobalt site,the transformation of a dimeric to a monomeric cobalt complex occurs,which involves the migration of a phenolate group.During the conversion,a P–P bond was cleaved and converted to phosphide and phosphinite.Current Co–P metal–ligand cooperativity presented in this work has been explored structurally,spectroscopically and theoretically.展开更多
Metal-nitrenes are critical intermediates in the incorporation of nitrogen functional groups,and a better understanding of the mechanism of their formation from the corresponding organoazide adducts is highly desirabl...Metal-nitrenes are critical intermediates in the incorporation of nitrogen functional groups,and a better understanding of the mechanism of their formation from the corresponding organoazide adducts is highly desirable.In this work,we demonstrate a new mode of organoazide deazotation at a phosphidecontaining(PPP)Co scaffold.展开更多
文摘A novel cobalt system featuring a Co–P moiety has been synthesized to study its metal–ligand cooperativity.A reversible conversion of a phosphide group to a P–P bond found in a dimeric cobalt(Ⅰ)complex involves electron transfer between Co and P,in which a single electron transfer is successfully coupled with a redox change in each cobalt ion.Upon coordination of aπ-acidic ligand such as acetonitrile and isocyanide at the cobalt site,the transformation of a dimeric to a monomeric cobalt complex occurs,which involves the migration of a phenolate group.During the conversion,a P–P bond was cleaved and converted to phosphide and phosphinite.Current Co–P metal–ligand cooperativity presented in this work has been explored structurally,spectroscopically and theoretically.
基金supported by the National Research Foundation of Korea(2020R1A2C3007364,2022M3C1A3092056 to Y.L.).We thank Dr Heui Beom Lee for helpful discussions and Dr Sugyeong Hong and Dr Sun Hee Kim at Korea Basic Science Institute for EPR analysis.
文摘Metal-nitrenes are critical intermediates in the incorporation of nitrogen functional groups,and a better understanding of the mechanism of their formation from the corresponding organoazide adducts is highly desirable.In this work,we demonstrate a new mode of organoazide deazotation at a phosphidecontaining(PPP)Co scaffold.
