The photodecarboxylation of [N,N-bis(2-pyridylmethyl)amino acidato]phenanthrolinecobalt(III) complexes: – formation and decomposition of metallacyclic species

摘要: Photolysis of [N,N-bis(2-pyridylmethyl)amino acidato]phenanthrolinecobalt(III) complexes (amino acidato = glycinato (dpg) or alaninato (dpa) 2-cyclopropylglycinato (dpc)) with UV light led to elimination carbon dioxide from the amino acidato chelate and formation cobalt(III) which contain a Co–C–N metallacycle. These photolysis products were characterised by NMR UV-vis spectroscopy and, in case dpg, X-ray crystallography. The eventual decomposition reactions monitored both D2O dilute DCl. included bis(2-pyridylmethyl)amine (bpa) an aldehyde derived atom metallacycle its alkyl substituents. A μ-peroxo dinuclear complex, [(bpa)(phen)(Co(O2)Co(phen)(bpa)]4+, was formed structure determined Experiments cyclopropyl derivative demonstrate that any intermediates radical centre on what α-carbon acid must be very short-lived.