207514-11-2Relevant academic research and scientific papers
The cleavage of coordinated heterocumulenes. The reactions of [Fe(CO)2(PPh3)2(η-SCY)] and their analogues with [Co(η-C5H5)(PPh3)2] to give heteronuclear [{Co(η-C5H5)}2{Fe(CO)2(PPh 3)}(μ3-S)(μ3-CY)] (Y=S or SR+)
Manning, Anthony R.,O'Dwyer, Liam,McArdle, Patrick A.,Cunningham, Desmond
, p. 139 - 149 (1998)
The reaction of [Fe(CO)2(PPh3)2(η2-CS 2)] with two equivalents of [Co(η-C5H5)(PPh3)2] gives [{Co(η-C5H5)}2{Fe(CO) 2(L)}(μ3-S)(μ3-CS)] (L=PPh3) as the sole product in good yield. Under the same conditions, [Fe(CO)2(L)2(η2-CS2Me)][SO 3CF3] gives [{Co(η-C5H5)}2{Fe(CO) 2(L)}(μ3-S)(μ3-CSMe)][SO 3CF3]. The PPh3 ligand of [{Co(η-C5H5)}2{Fe(CO) 2(L)}(μ3-S)(μ3-CS)] (L=PPh3) may be replaced by P(OPh)3 and P(OMe)3 on UV photolysis to give the complexes where L=P(OPh)3 and P(OMe)3, but no isolable products were formed when L=CO, CNMe, PMe3 or PBu3n. The three clusters react with RI and ROSO2CF3 (R=Me, Et or allyl) to give [{Co(η-C5H5)}2{Fe(CO) 2(L)}(μ3-S)(μ3-CSR)]+ salts, and there is spectroscopic evidence for the formation of the [{Co(η-C5H5)}2{Fe(CO)2(PPh 3)}(μ3-S)(μ3-CSMe2)] 2+ cation. The molecular structures of [{Co(η-C5H5)}2{Fe(CO)2(PPh 3)}(μ3-S)(μ3-CS)] and [{Co(η-C5H5)}2{Fe(CO)2(PPh 3)}(μ3-S){μ3-CSMe}][I] have been determined by X-ray diffraction methods, and shown to be based on a Co2Fe triangle capped on one face by a μ3-S ligand and on the other face by a μ3-CS or μ3-CSMe+ ligand acting as a two-electron donor to the cluster. In the salt there are two cations whose structures differ slightly. In general, bond lengths are normal, but those to iron are always longer than those to cobalt.
Substitution reactions of [{Co(η5-C5H5)}2 {Fe(CO)2(PPh3)}(μ3-S) (μ3-CS)]
Manning, Anthony R,Palmer, Anthony J
, p. 60 - 65 (2007/10/03)
On heating, the cluster [{Co(η5-C5H5)}2{Fe(CO)2(PPh3)}(μ3-S) (μ3 -CS)], 1a, reacts with PR3 ligands (R = (b) MeO, (c) PhO and (d) Bun) by replacement of PPh3 to give [{Co(η5-C5H5)}2{Fe(CO)2(PR3)} (υ3-S)(μ3-CS)], 1b-d, and with CNR (R = (e) Me, (f) 2,4,6-Me3C6H2 and (g) 2,6-Cl2C6H3) by replacement of PPh3 and then CO to give [{Co(η5-C5H5)}2{Fe(CO)2(CNR)}(μ3-S)(μ3-CS)], 1e-g, and [{Co(η5-C5H5)}2{Fe(CO)(CNR)2}(μ3-S)(μ3-CS)], 2e-g. These reactions are successful only under a very limited range of conditions, i.e. with a large excess of the incoming ligand and very short reaction times and/or moderate temperatures. The CO ligands in [{Co(η5-C5H5)}2{Fe(CO)2(CNR)}(μ3-S)(μ3-CS)] are labile and may be replaced by more CNR in a reversible reaction or by PPh3 to give, respectively, [{Co(η5-C5H5)}2{Fe(CO)(CNR)2}(μ3-S)(μ3-CS)], 2e-g, and [{Co(η5-C5H5)}2{Fe(CO)(CNR)(PPh3)}(μ3-S)(μ3-CS)], 2h (R = 2,6-Cl2C6H3). The IR spectra of the clusters have been studied and for the first time the absorption band in each due to the ν(CS) vibration of the μ3-CS ligand has been identified unambiguously. Its frequency depends on the FeL3 ligand set in a predictable way and lies in the range 1022-1041 cm-1. In the 13C-NMR spectra the μ3-C atom gives rise to resonances between δ 354 and 359. The clusters do not undergo bridge terminal ligand site exchange. In particular, there is no evidence for the formation of isomers, which contain terminal CS and μ3-CNR ligands.
