A. Kasem. Chowdhury

Generation and reactions of tricarbonylferrate(1-) anion radical in a flowing afterglow apparatus

Generation a partir de Fe(CO) 5 et etude des reactions ion-molecule de (OC) 3 Fe − avec de petites molecules neutres (H 2 , N 2 , H 2 C=CHCH 3 , C 2 H 2 , etc)

Generation and ion-molecule reactions of ethyl diazoacetate anion radical (EtO2CCHN2XXX)

Abstract Thermal electron attachment to EtO 2 CCHN 2 produced the parent anion radical EtO 2 CCHN 2 -( m/z 114). The ion-molecule reactions of m/z 114 with 30 neutral substrates were examined. Using the bracketing method, PA(EtO 2 CCHN 2 XXX ) = 355±4 kcal mol -1 was determined. The reaction of m/z 4 with CH 3 SH produced H 2 CS XXX , the product of β-elimination of H + 2 from the thiol. From a series of bracketing studies and determination of the equilibrium constant for the electron transfer (ET) process CH 3 C(O)C(O)CH 3 - +EtO 2 CCHN 2 = CH 3 C(O)C(O)CH 3 +EtO 2 CCHN 2 XXX EA(EtO 2 CCHN 2 ) = 19.7 kcal mol -1 was derived. Both associative and dissociative ET were observed in the reactions of m/z 114 with certain perhalomethanes (depending on their EA) as well as halogen-atom abstraction from BrCCl 3 . While no reaction was observed between m/z 114 with CH 3 CHO or (CH 3 ) 2 CO, m/z 114 reacted with certain other ketones and esters (CF 3 CO 2 R) mainly to yield enolate anions of the β-keto esters, EtO 2 CCHC(O - )R. These enolate anions are believed to be formed by nucleophilic addition of C α of m/z 114 to the carbonyl group of the neutral substrate followed by loss of N 2 and radical β-fragmentation.