REACTIONS OF POLYNUCLEAR METAL-CARBONYL ANIONS WITH THE PROTON AND WITH CARBOCATION REAGENTS - O-PROTONATION AND O-ALKYLATION OF BRIDGING CARBONYL LIGANDS

Reactions of [Fe3(CO)11]2- with electrophiles R=CH3+, CH3CH2+, and CH3C(=O)+ lead to the O-alkyl or O-acetyl derivatives Fe3(CO)10(COR)-. Similarly, the reaction of HFe3(CO)11- with CH3+, C2H5+, or H+ gives HFe3(CO)10(COCH3), HFe3(CO)10(COCH2CH3), and HFe3(CO)10(COH), respectively. Variable-temperature 13C NMR spectra of [PPN]2[Fe3(CO)11], [PPN] [Fe3(CO)10(COCH3)], HFe3(CO)10(COCH3), and [PPN][Fe3(CO)10(COC(⩵O)CH3)] demonstrate several different CO permutation rates within each molecule. The alkyl or acyl carbon atom of Fe3(CO)10(COR)- is attacked by C6H5S- in preference to attack at the iron-coordinated carbon. © 1979, American Chemical Society. All rights reserved.