Synthesis, structure and formation pathways of new Fe–S complexes containing [Fe2S2]-units in different valences, [Fe2S2(CO)4(PPh3)2], [Fe3S2(CO)6(PPh3)3] and [Fe4S2(CO)10]2− and the origin of the [Fe2S2]-unit in metal–[Fe2S2(CO)6] complexes

Zhuang, Bin; Li, He; Chen, Jiutong; Zhou, Zhangfeng; Wu, Kechen

doi:10.1016/j.jorganchem.2004.05.036

Cited by 8 publications

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References 30 publications

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“…The structure of 2 has also been reported by Gao et al Compared to 1 , the Fe–CO bonds in 2 are shorter by 0.05 Å, consistent with strengthened π bonding. Curiously, a valence isomer of 3 , the diferrous sulfide Fe 2 (μ-S) 2 (CO) 4 (PPh 3 ) 2 ( 2* ), has also been claimed on the basis of X-ray crystallography, but we see no evidence for such a species.…”

Section: Resultsmentioning

confidence: 99%

Redox and “Antioxidant” Properties of Fe₂(μ-SH)₂(CO)₄(PPh₃)₂

Kagalwala

Lalaoui

et al. 2019

Inorg. Chem.

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The chemistry of Fe 2 (μ-SH) 2 (CO) 4 (PPh 3) 2 (2 HH) is described with attention to S-S coupling reactions. Produced by reduction of 2 (Fe 2 (μ-S 2)(CO) 4 (PPh 3) 2), 2 HH is an analogue of Fe 2 (μ-SH) 2 (CO) 6 (1 HH) that exhibits well-behaved S-centered redox. Both 2 HH and the related 2 MeH exist as isomers that differ with respect to the stereochemistry of the μ-SR ligands (R = H, Me). Compounds 2 HH , 2 MeH , and 2 protonate to give rare examples of Fe-SH-hydrides and Fe-S 2hydrides. Salts of [H2] + , [H2 HH ] + , and [H2 MeH ] + were characterized crystallographically. Complex 2 HH reduces O 2 , H 2 O 2 , (PhCO 2) 2 , and Ph 2 N 2 giving 2. Related reactions involving 1 HH gave uncharacterizable polymers. The differing behaviors of 2 HH vs 1 HH reflects the stabilization of the ferrous intermediates by the PPh 3 ligands. When independently generated by reaction of 2 HH with TEMPO, 2* quantitatively converts to 2 or, in the presence of C 2 H 4 , is trapped as the ethanedithiolate Fe 2 (μ-S 2 C 2 H 4)(CO) 4 (PPh 3) 2. Evidence is presented that the Hieber-Gruber synthesis of 1 involves polysulfido intermediates [Fe 2 (μ-S n) 2 (CO) 6 ] 2-(n > 1). Two relevant experiments are: (i) protonation of [Fe 4 (μ-S) 2 (μ-S 2)CO) 12 ] 2gives 1 and 1 HH and (ii) oxidation of 1 HH by sulfur gives 1.

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Section: Resultsmentioning

confidence: 99%

Redox and “Antioxidant” Properties of Fe₂(μ-SH)₂(CO)₄(PPh₃)₂

Kagalwala

Lalaoui

et al. 2019

Inorg. Chem.

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“…[7] A trinuclear tris(triphenylphosphane) complex has also recently been prepared in approximately 30 % yield by the treatment of disulfide 6c with LiEt 3 BH in the presence of triphenylphosphane and CuCl·PPh 3 or AgNO 3 ·PPh 3 . [8] On protonation [9][10][11][12][13] with excess triflic acid in CH 2 Cl 2 solution, complex 2 gave the bridged hydride species 3. Complexes 2 and 3 were characterized by IR and NMR spectroscopy and CV studies.…”

Section: Resultsmentioning

confidence: 99%