Synthesis and cluster interconversion chemistry of a linear trinuclear hexakis(μ-benzenethiolato)triiron(II) hexacarbonyl compound

Marc Walters, John C. Dewan

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Abstract

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) Å, b = 10.488 (1) Å, c = 19.052 (2) Å, β = 95.41 (6)°, V = 2203.52 Å3, 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.

Original languageEnglish (US)
Pages (from-to)4889-4893
Number of pages5
JournalInorganic Chemistry
Volume25
Issue number27
StatePublished - 1986

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Carbon Monoxide
chemistry
synthesis
iron
Iron
ligands
inert atmosphere
Ligands
Crystals
carbon monoxide
crystals
self assembly
enzymes
ethyl alcohol
sulfur
Sulfur
Self assembly
atmospheres
Ethanol
irradiation

ASJC Scopus subject areas

  • Inorganic Chemistry

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Synthesis and cluster interconversion chemistry of a linear trinuclear hexakis(μ-benzenethiolato)triiron(II) hexacarbonyl compound. / Walters, Marc; Dewan, John C.

In: Inorganic Chemistry, Vol. 25, No. 27, 1986, p. 4889-4893.

Research output: Contribution to journalArticle

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abstract = "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) {\AA}, b = 10.488 (1) {\AA}, c = 19.052 (2) {\AA}, β = 95.41 (6)°, V = 2203.52 {\AA}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.",
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N2 - 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) Å, b = 10.488 (1) Å, c = 19.052 (2) Å, β = 95.41 (6)°, V = 2203.52 Å3, 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.

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