97042-28-9Relevant academic research and scientific papers
Iron and molybdenum methylidene compounds (C5H5)(CO)2FeCH2+ and (C5H5)(CO)3MoCH2+PF 6- as alkylating agents toward vinyl, allyl, and acetyl ligands. Preparation and characterization of a molybdenum (methyleneoxy)ethylidene iron compound, (C ...
Bodnar,Cutler
, p. 1558 - 1565 (2008/10/08)
Full title: Iron and molybdenum methylidene compounds (C5H5)(CO)2FeCH2+ and (C5H5)(CO)3MoCH2+PF 6- as alkylating agents toward vinyl, allyl, and acetyl ligands. Preparation and characterization of a molybdenum (methyleneoxy)ethylidene iron compound, (C5H5)(CO)(PPh3)FeC(CH3)OCH 2Mo(CO)3(C5H5)+PF 6-. The methylidene complexes Cp(CO)2Fe=CH2+ (1) and Cp(CO)3MoCH2+PF6- (2) are used as alkylating agents toward coordinated ligands. Thus, 1 adds to the uncoordinated double bonds of FpCH=CH2 and FpCH2CH=CH2 (Fp = Cp(CO)2Fe) to give the homologated Fp2 salts [FpCH2]2CH+ and Fp[CH2= CHCH2CH2Fp]+. The former salt arises from electrophilic attack of 1 on the vinylic β-carbon, followed by isomerization of the resulting alkylidene intermediate FpCH+CH2CH2Fp to the observed Fp2 β-carbonium ion salt. The acetyl complex Cp(CO)(PPh3)FeCOCH3 (4), but not FpCOCH3, also undergoes alkylation by 1. A partially characterized [(methyleneoxy)ethylidene]iron, Cp(CO)(PPh3)FeC(CH3)OCH2Fp+ (16), results that readily degrades to the μ-acetyl compound Cp(CO)(PPh3)FeC(CH3)OFp+PF6 - as the major product. Use of the more electrophilic 2 converts 4 to the fully characterized adduct Cp(CO)(PPh3)-FeC(CH3)OCH2Mp+PF 6- (5) (Mp = Cp(CO)3Mo). Reactions of nucleophiles (I-, Cl-, various hydride donors) with 5 displace the starting acetyl complex 4 and leave the corresponding molybdenum methyl complex.
