Iron, cobalt and vanadium complexes of the N(CH2CH2S)33− ligand with chloride, azide, cyanide and carbonyl co-ligands
| Autor: | Raymond L. Richards, Sian C. Davies, David L. Hughes, Marcus C. Durrant, J. Roger Sanders |
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| Rok vydání: | 2000 |
| Předmět: | |
| Zdroj: | Journal of the Chemical Society, Dalton Transactions. :4694-4701 |
| ISSN: | 1364-5447 1470-479X |
| DOI: | 10.1039/b006591i |
| Popis: | Reaction of [Fe(acac)3], Et4NCl and N(CH2CH2SH)3 (NS3H3) in MeCN gave [Et4N][FeCl(NS3)] 1 and metathesis the azide [Et4N][Fe(N3)(NS3)] 2, but reaction of [Fe(acac)3], R4NOAc and NS3H3 in MeCN gave [R4N][Fe4(NS3)3] (R = Et, 3; Me, 4). Complex 1 is reduced under various conditions giving R′[Fe(NS3)] (R′ = Et4N, 5; Tl, 6; N2H5, 7) which probably contain sulfur-bridged [{Fe(NS3)}n]n− anions. Under CO, 1 is reduced to the paramagnetic [Et4N][Fe(NS3)(CO)] 8 from which Tl[Fe(NS3)(CO)] 9 may be made by metathesis. Compound 8 reacts with metal chlorides in acetonitrile giving trinuclear [M{Fe(NS3)(CO)}2-S,S′] (M = Fe, 10; Co, 11). The above complexes were characterised by microanalysis, IR and Mossbauer spectra and magnetic measurements; crystal structure determinations were carried out on 1, 2, 8, 10, and 11. The properties of the anions of 1 and 8 and of the hypothetical anions [Fe(NS3)]− and [Fe(N2)(NS3)]− have been investigated by density functional theory calculations. Compounds 8 and 10 have ν(CO) in the range 1960–1880 cm−1 and model aspects of carbon monoxide binding to the cofactor of nitrogenase. Related cyanide complexes [Et4N][M(NS3)(CN)] (M = Co, 12; V, 13) have been characterised, 12 by X-ray analysis. |
| Databáze: | OpenAIRE |
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