Iron complexes thiocarbonyls

Functionalization of a thiocarbonyl ligand occurs during the nucleophilic attack on a cyclopentadienyl iron complex by aziridine. 

The reductive behavior of iron-carbene porphyrins has been investigated. A 2g + FI" " reduction of thiocarbonyl complexes can lead to the corresponding thioformyl complexes in a reversible system [421]. 

Thiocarbonyl (see Thiocarbonyl) compounds react rapidly with iron carbonyls, but only in a few cases are mononuclear )] -C=S complexes reahzed. Most of the work in this area has resulted from the discovery that carbon disulfide reacts with iron carbonyl transfer agents, in the presence of phosphines or phosphites, to give complexes (127). In several of these cases, it is possible to exchange one or both of the phosphine/phosphite ligands in high yield. 

High yields of Cr(CO)5(CX) (X = S, Se) are obtained by displacement of the arene ligands in (>/ -arene)Cr(CO)2(CX) with CO under 10 kPa . Reduction of CljCS by (tetraphenylporpinato)iron(II) in the presence of Fe powder leads to the five-coordinated species, (tetraphenylporphinato)(thiocarbonyl)iron(II) . The same complex, as well as the analogous selenocarbonyl derivative, can also be obtained by the decomposition of Fe(II) porphyrin thio- and selenocarbene species . 

Addition of alkylthiolates to porphyrin-iron-carbene complexes immediately gave new complexes characterized by their hyperporphyrin spectra [100]. Similar spectra were obtained with the analogous iron thiocarbonyl complexes [103], suggesting that these complexes have similar electronic structures. 

Molecular rotation in the cavity has been discussed for many compounds using nmr(8,9), esr(lO) and Mossbauer spectroscopy(4,5). A complete description of the Mossbauer spectrum for such a case has been given by Gibb(4) for that of the 3 1 clathrate of thiocarbonyl diamide and bis( -cyclopentadienyl)iron(II). Evidence for conformational isomerism has been presented recently based on the ir spectra of y-cyclopentadienylmetal carbonyl complexes such as CpFe(CO) SiCl Me(ll), ip -MeC H Mn(CO) (P(OMe) )(12) and others(13), and on the Mossbauer... 

---