460718-11-0Relevant articles and documents
The reaction of [{Co(η5-C5 H5)}2{Fe(CO)2(PPh3)} (μ3-S)(μ3-CS)] and related complexes with carbon disulfide (see abstract)
Manning, Anthony R.,McAdam, C. John,Palmer, Anthony J.,Robinson, Brian H.,Simpson, Jim
, p. 4472 - 4481 (2003)
[{Co(η5-C5H5)}2{Fe(CO) (L)2}(μ3-S)(μ3-CS)] complexes 1 where (L)2 = (a) (CO)(PPh3), (b) (CO) {P(OPh)3}, (c) (CO)(PBu3n), (d) (CNMe)2 and (e) (CNMes)2 (Mes = 2,4,6-Me3C6H2), but not (CO)(CNMes), react with CS2 under reflux to give [{Co(η5-C5 H5)}2{Fe(L)2}(μ3-S) (μ3-C2S3)], 2, in which a CS2 molecule has been incorporated into a FeSC(S*)SC heterocycle with a trithiocarbonate moiety bridging the Fe-C cluster edge. Clusters 2 react with incoming ligands either by simple ligand substitution, or by displacement of CS2 to form clusters of type 1. The exocyclic sulfur atom S* is nucleophilic and with electrophiles E forms [{Co(η5-C5H5)}2 {Fe(L)2}(μ3-S)(μ3-C2 S3E] adducts which contain S*→E bonds where E = Me+ [3]+, Et+ [4]+, HgCl2 [5], and I4 (or I+) [6]. The clusters 2a-c and the [3]+ and [4]+ derived from them are chiral as indicated by their NMR spectra, and do not racemize on the NMR timescale. The structures of 2a·2C6H6 and [3a]I·C6H6·CHCl3 are reported. Cluster 2a contains a very short Fe-Cμ bond as compared with 1a, and it is suggested that in many respects the FeSC(S)SCμ ring is best regarded as a metallo-1,3-dithiole-2-thione (or metallovinyl trithiocarbonate) with a Fe-Cμ double bond which, on alkylation at the exocyclic S*, adopts a more delocalised electronic structure with a longer Fe-Cμ bond. Spectroscopic and electrochemical data for the new compounds are discussed.
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.
