61332-94-3Relevant academic research and scientific papers
Gas-phase ligand substitution reactions with (OC)Fe(NO)2.-', (OC)2Co(NO).-, (η3-C3H5)Co(CO)2.-, (C3H5)Co(CO)3.-, and CpCo(CO)2.-
McDonald, Richard N.,Schell, Philip L.
, p. 1806 - 1820 (2008/10/08)
Three 17-electron transition-metal complex negative ions LM(CO)x-1.- ((OC)Fe(NO)2.-, (OC)2Co(NO).-, and (η3-C3H5)Co(CO)2.-) and two parent molecular anion radicals LM(CO)x.- ((C3H5)Co(CO)3.- and CpCo(CO)2.-) were generated by electron impact on the corresponding LM(CO)x complexes in the gas phase. The ion-molecule reactions of these five metal complex negative ions were studied with the neutral molecules PF3, PMe3, NO, SO2, olefins with electron-donating and -withdrawing vinyl substituents, acetone and certain fluorinated derivatives, biacetyl, O2, CO, and CS2. In general, the LM(CO)x-1.- complexes and CpCo(CO)2.- reacted by ligand substitution involving the associative mechanism. In many cases, the product ions of adduct formation and ligand substitution were directly observed in the same reaction. These ligand substitution reactions appear to take advantage of the abbility of the NO, η3-C3H5, and Cp ligands to reduce their hapticities as the neutral ligand bonds to the metal. The reaction of (C3H5)Co(CO)3.- with PF3 occurred by fragmentation of the allyl radical. This latter result was considered to occur by radical β-fragmentation of the excited acyl complex [C3H5C(=O)Co(CO)2(PF3) .-]* formed by CO insertion into the Co-allyl bond. Both parent molecular anion radicals were observed to undergo electron transfer with several of the neutral substrates yielding EA((η3-C3H5)Co(CO)3) = EA(CpCo(CO)2) = 0.62 ± 0.1 eV; EA(η3-C3H5)Co(CO)2) = 0.9 ± 0.2 eV was also measured. The results of the reactions of the parent LM(CO)x.- species with the neutral ligands were consistent with their structures having a 17-electron configuration about the metal with η3-Cp and η1-C3H5 ligands.
