Iron, thiocarbonyl

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. 

If bromine is used in equation 8, carbon tetrabromide [558-13-4] is formed. With a minor amount of iodine present, and in the absence of iron catalyst, carbon disulfide and chlorine react to form trichioromethanesulfenyl chloride (perchloromethyl mercaptan [594-42-3]), CCI3SCI, which can be reduced with staimous chloride or tin, and hydrochloric acid to form thiophosgene (thiocarbonyl chloride [463-71-8], CSCI2, an intermediate in the synthesis of many organic compounds (see Sulfurcompounds). 

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]. 

When heated in a closed vessel to 200° C., thiocarbonyl tetrachloride decomposes with formation of sulphur chloride. It dissolves chlorine without being attacked. Water at 160° C. decomposes it entirely into carbon dioxide, hydrogen chloride and sulphur. It is also decomposed at ordinary temperatures by contact with metallic iron, the products being ferrous chloride and carbon tetrachloride,5 although according to de Fazi5 the reaction may, under special conditions, proceed according to the equation ... 

There is some debate as to whether this is the first report of sulfines as dipoles, and indeed this article mentions two precedents from Block and Schaumann-Walter. The article reports some factors which may help to explain why it took so long to find unequivocal examples of the dipolar activity of sulfines. At the end of this review it is noteworthy and ironic that the solution to this long-standing search was a reaction with a thiocarbonyl compound ... 

DICARBONYL(iis-CYCLOPENTADIENYL)(THIO-CARBONYL)IRON(l +) HEXAFLUOROPHOSPHATE(l -) AND DICARBONYL(iis-CYCLOPENTADIENYL)-[(METHYLTHIO)THIOCARBONYL]IRON... 

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 . 

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

Carbon monoxide binds weakly as a cr-donor ligand to four-coordinate co-balt(II) systems. Despite a bout of artifactual excitement, CO has never been observed to bind significantly to five-coordinate Co systems with a nitrogenous axial base to yield octahedral six-coordinate species. - The sulfur analogue thiocarbonyl (CS), although not stable as a free entity, binds very strongly to iron-porphyrin species in a linear manner. ... 

THIOCARBONYL TETRACHLORIDE (594-42-3) Contact with alkalis or amines can cause rapid decomposition. Contact with hot iron or steel produces toxic carbon tetrachloride fumes. Hot water or steam produces hydrochloric acid. Reacts with sulfur, and carbon dioxide. Attacks some plastics, rubber, and coatings. Corrosive to most metals. 

The glycosidase-inhibitory properties of sugar-shaped cyclic thioureas were first, explored by Lehmann and co-workers,414 who obtained the hexa-hydropyrimidine-2-thione glucomimetic 271 by thiocarbonylation of the diamine precursor 270. Compound 271 was a very weak inhibitor of sweet-almond /3-glucosidasc, and this was ascribed to the lack of the OH group at the homologous position of C-3 in n-glucopyranosidcs. Moreover, an unexpected preference for the irons-diaxial conformation in deuterium oxide solution. was observed (Scheme 73). 

Selective generation of various carbanions from thioamides is achieved probably because the thiocarbonyl group finely attenuates the acidity in the compounds. One of the most well known groups of carbanions are the enethi-olates, which are formed by deprotonation at the position a to the thiocarbonyl group in thioamides. Potassium f-butoxide is used to deprotonate thioacetamide 63, and then arylation and alkylation with iodobenzene and iodoadamantane are carried out in the presence of a catalytic amount of FeBr2 (Eq. 20) [44l. The reaction is believed to involve the iron enethiolate. 

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