Tricarbonylferrole iron tricarbonyl derivatives: formation from thiophenes and iron atoms in a CO atmosphere and fluxional behaviour

Abstract

TRISTRAM CHIVERS and PETER L. TIMMS. Can. J. Chem. 55,3509 (1977).Co-condensation of metal atoms (Cr, Fe) with thiophenes R 'SARI (R = R r = H, Me; R = H, R' = Me) at -196°C leads to desulphurization of the thiophene. Warm-up of the iron-thiophene co-condensate in a CO atmosphere produces derivatives of tricarbonylferrole iron tricarbonyl, C4H2RR'Fe2(C0)6. 13C nmr studies of these complexes show that the tricarbonyl ferrole unit is static from -95°C to + 60°C, while the R -F~( C O )~ group exhibits fluxional behaviour. Addition of dienes or Me3P in hexane to the iron-thiophene co-condensate at -196°C yields thermally unstable red solutions on melting.TRISTRAM CHIVERS et PETER L. TIMMS. Can. J. Chem. 55,3509 (1977).La co-condensation d'atomes de metaux (Cr, Fe) avec les thiophenes R (R = R' = H, Me; R = H, R' = Me) a -196"C, conduit a la desulfuration de ces derniers.Le rechauffement du compost5 co-condense thiophenefer dans un atmosphere de CO, conduit aux dtrives du tricarbonyle tricarbonylferrole-fer C4H2RRfFe2(CO),. Les etudes par rmn du 13C de ces complexes montre que la partie tricarbonylferrole est statique de -95°C a + 60°C, alors que le groupe ~c-Fe(C0)~ presente un comportement variable. L'addition de diknes ou du Me3P dans l'hexane au compost co-condenst thiophene-fer a -196"C, conduit par fusion a des solutions rouges, thermiquement instables.[Traduit par le journal]

Deoxygenation and desulfurization of organic compounds via transition metal atom cocondensation

“…Skell has reported that cyclic thioethers are desulfurized and dehydrosulfurized when reacted with singlet carbon atoms,19 and the desulfurization of thiophenes upon cocondensation with chromium and iron has been noted. 23 Recently, Billups and Margrave24 have found that the cocondensation of dimethyl ether with calcium, barium, strontium, or iron, followed by removal of excess dimethyl ether and hydrolysis of the reactor residue, results in the formation of appreciable quantities of Cj-Cg hydrocarbons.…”

Metal vapour synthesis and conformational analysis of bis(2-trimethylsilyl-3-methylphosphobenzene)

“…Early attempts of reactions between metal vapours and heterocyclic compounds demonstrated difficulties posed by the heteroatom for the synthesis of organometallic complexes: Timms 1 found that the reaction between iron and thiophene gave only one isolable product, the metallocyclopentadiene compound as a tricarbonyl adduct, by allowing the reaction mixture to warm up in a carbon monoxide (CO) atmosphere (Eqn [1]); in the absence of added CO or in the presence of other possible ligands, such as dienes or phosphines, no compounds were isolated.…”