57763-33-4Relevant academic research and scientific papers
Synthesis and cluster interconversion chemistry of a linear trinuclear hexakis(μ-benzenethiolato)triiron(II) hexacarbonyl compound
Walters, M. Anton,Dewan, John C.
, p. 4889 - 4893 (2008/10/08)
The neutral compound Fe3(SPh)6(CO)6 (1) assembles in a solution containing NaSPh and FeCl2 in a 2:1 ratio in ethanol under an atmosphere of carbon monoxide at room temperature. It also forms in the reaction of the Fe4(SPh)102- ion with CO and FeBr2 and by the oxidative addition of PhSSPh to an Fe(0) carbonyl species with UV irradiation in an inert atmosphere under ambient conditions. Product 1 was characterized by X-ray diffraction and found to be a linear trinuclear complex in which the benzenethiolate ligands occupy bridging positions and the carbonyl ligands are exclusively terminally bonded. Crystal data are space group P21/n with a = 11.077 (1) ?, b = 10.488 (1) ?, c = 19.052 (2) ?, β = 95.41 (6)°, V = 2203.52 ?3, and Z = 2. On the basis of the observed octahedral coordination of each of the iron atoms in 1, it is suggested that octahedral coordination may occur in the limit of unrestricted CO binding in the CO-inhibited states of iron-sulfur enzymes. Compound 1 converts to Fe(SPh)42- (2) in neat Me2SO solution where the counterion is probably Fe(Me2SO)62+. The compound [Fe(Me2SO)6][Fe4(SPh)10] (3) is formed in a mixed solution of Me2SO/THF (1:25, v/v) and can be isolated as brown crystals. The self-assembly of these clusters in lieu of others that could form with the same Fe:thiolate ratio suggests that those which are obtained represent clusters with particularly stable structures. The formation of clusters in such stoichiometrically free environments suggests new approaches to the study of cluster formation.
Improved syntheses of [Fe2S2Cl4]2- and [Fe2OCl6]2- and oxo/sulfido ligand substitution by use of silylsulfide reagents
Do,Simhon,Holm
, p. 3809 - 3812 (2008/10/08)
New syntheses of [Fe2S2Cl4]2- (1) and [Fe2OCl6]2- (2) and terminal oxo/sulfido ligand substitution reactions have been devised with use of the reagents (Me3Si)2S (3), NaSSiMe3 (4), and NaOSiMe3 (5) in acetonitrile solutions. The preparation of 4 is described. Reactions of (Et4N)[FeCl4] with equimolar quantities of 3, 4, and 5 in acetonitrile afford the Et4N+ salts of 1 (76%, 77%) and 2 (66%), respectively, in good yields. In THF (Et4N)2(1) was isolated in essentially quantitative yield from a reaction using 3. Equimolar amounts of 2 and 3 give partial conversion to 1 in a bridge oxo/sulfido substitution reaction; a competing reaction is that of product Me3SiCl with 2 to form [FeCl4]-. The chelate complex VO(acen) reacts with excess 3 to give a quantitative in situ yield of VS(acen). On a preparative scale a 79% yield was obtained. Similarly, NbO(S2CNEt2)3 was converted to yellow NbS(S2CNEt2)3 (νNbS = 493 cm-1) in 52% isolated yield. These syntheses of 1 and 2 in particular offer advantages over previous methods. The results presented suggest that silylsulfide reagents may have extended utility in effecting bridging and terminal oxo/sulfido transformations.
