Chemistry of Tetrasulfur Including Mysterious Rectangular S4 Metal Complexes

Isobe, Kiyoshi

doi:10.1246/cl.2011.1060

Cited by 3 publications

(2 citation statements)

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“…However, if the molecule is floppy, then rigorous calculations of rovibrational states on accurate potential energy surface is needed for prediction of the spectrum and meaningful computation of the partition function. Importantly, electronic structure calculations of potential energy surface for S 4 showed that it is floppy (33,34,38,39). It has a single bond in the middle, consistent with its formation process:…”

Section: Production Of Smentioning

confidence: 69%

Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

Babikov

2017

Proc. Natl. Acad. Sci. U.S.A.

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A hierarchy of isotopically substituted recombination reactions is formulated for production of sulfur allotropes in the anoxic atmosphere of Archean Earth. The corresponding system of kinetics equations is solved analytically to obtain concise expressions for isotopic enrichments, with focus on massindependent isotope effects due to symmetry, ignoring smaller mass-dependent effects. Proper inclusion of atom-exchange processes is shown to be important. This model predicts significant and equal depletions driven by reaction stoichiometry for all rare isotopes: 33 S, 34 S, and 36 S. Interestingly, the ratio of capital Δ values obtained within this model for 33 S and 36 S is −1.16, very close to the mass-independent fractionation line of the Archean rock record. This model may finally offer a mechanistic explanation for the striking mass-independent fractionation of sulfur isotopes that took place in the Archean atmosphere of Earth.S-MIF | mass-independent fractionation | Archean atmosphere | sulfur recombination | isotope effect M ass-independent fractionation of sulfur isotopes (S-MIF) in the Archean rock record (1-6) serves as strong evidence of an anoxic atmosphere (7-9), indicating a low-oxygen gasphase chemistry before 2.3 billion y ago. However, the actual chemical process, or processes, responsible for generation of significant enrichments of sulfur-bearing species in heavy isotopes of sulfur, and leading to mass-independent fractionation, still remains unidentified. Some mass-independent fractionation was observed experimentally in SO 2 photolysis (10-12) and in nonadiabatic dynamics of SO 2 photodissociation (13,14). Another important chemical pathway, specific to a low-oxygen atmosphere (7,8,(15)(16)(17), is a chain of recombination reactions that start from recombination of photolytically produced sulfur atoms (S + S → S 2 ), go through formation of larger sulfur allotropes (S + S 2 → S 3 , S 2 + S 2 → S 4 , and S + S 3 → S 4 ), and end up at the elemental sulfur (S 4 + S 4 → S 8 ) that can be deposited, preserved, and could contribute to S-MIF in the Archean atmosphere. Unfortunately, experimental studies of gas-phase sulfur chemistry and photochemistry are complicated, and their results are often not entirely certain. Moreover, sulfur has four stable isotopes ( 32 S, 33 S, 34 S, and 36 S), which leads to a multitude of possible isotopic combinations of reagents and products in the recombination reactions listed above. It is unlikely that all these processes will be characterized experimentally at the required level of detail any time soon. Thus, it is desirable to analyze these reactions theoretically to determine whether a significant enrichment of rare sulfur isotopes is at all possible through these processes, and what steps are the most important.We build upon our experience (18-21) with the recombination reaction that forms ozone, O + O 2 → O 3 , and is known to produce significant mass-independent fractionation of oxygen isotopes 17 O). In this paper we attempt to export these two major ele...

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Section: Production Of Smentioning

confidence: 69%

Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

Babikov

2017

Proc. Natl. Acad. Sci. U.S.A.

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“…Polysulfide anions (S n 2– ) are classic examples of the catenation property of sulfur and are quite well-known in the literature. ,− The synthesis, structural diversity, and reactivity of an appreciable number of mono-, bi-, and poly nuclear compounds of polysulfide involving transition metals, lanthanides, and main group elements have been reported previously. − It may, however, be noted that most of these metal–polysulfido compounds are strictly organometallic compounds. − ,− ,− ,,,, While reports on several binuclear transition metal-polysulfido compounds are available in the literature, ,,,− the majority of these compounds are, however, metal sulfides and clusters with only S-donor ligands (HS – , S 2– , and S n 2– ). Representative examples of such clusters include [Cu 2 (S 3 )(S 4 )] 2– , [Ni 2 (μ-S 4 )] 2+ , [Ni 2 (μ-S 5 )] 2+ , [Co 2 (μ-S 4 )] 2+ , [Co 2 (μ-S 5 )] 2+ , [Fe 2 (μ-S 5 )] 2+ , [Fe 2 (μ-S 4 )] 2+ , [Fe 2 (μ-S) 2 (S 5 ) 2 ] 2– , [S 5 Fe(μ-S) 2 FeS 5 ] 2– , [Mn 2 (μ-S 4 )] 2+ , and [Mn 2 (μ-S 5 )] 2+ as well as few higher nuclearity clusters .…”

Section: Introductionmentioning

confidence: 97%

Generation and Reactivity of Polychalcogenide Chains in Binuclear Cobalt(II) Complexes

Hossain,

Roy Choudhury,

Majumdar

2024

JACS Au

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A series of six binuclear Co(II)−thiolate complexes, [Co 2 (BPMP)(S−C 6 H 4 -o-X) 2 ] 1+ (X = OMe, 2; NH 2 , 3), [Co 2 (BPMP)(μ-S−C 6 H 4 -o-O)] 1+ (4), and [Co 2 (BPMP)(μ-Y)] 1+ (Y = bdt, 5; tdt, 6; mnt, 7), has been synthesized from [Co 2 (BPMP)(MeOH) 2 (Cl) 2 ] 1+ (1a) and [Co 2 (BPMP)(Cl) 2 ] 1+ (1b), where BPMP 1− is the anion of 2,6-bis[[bis(2-pyridylmethyl)amino]methyl]-4-methylphenol. While 2 and 3 could allow the two-electron redox reaction of the two coordinated thiolates with elemental sulfur (S 8 ) to generate [Co 2 (BPMP)(μ-S 5 )] 1+ (8), the complexes, 4−7, could not undergo a similar reaction. An analogous redox reaction of 2 with elemental selenium ([Se]) produced [{Co 2 (BPMP)(μ-Se 4 )}{Co 2 (BPMP)(μ-Se 3 )}] 2+ (9a) and [Co 2 (BPMP)(μ-Se 4 )] 1+ (9b). Further reaction of these polychalcogenido complexes, 8 and 9a/9b, with PPh 3 allowed the isolation of [Co 2 (BPMP)(μ-S)] 1+ (10) and [Co 2 (BPMP)(μ-Se 2 )] 1+ (11), which, in turn, could be converted back to 8 and 9a upon treatment with S 8 and [Se], respectively. Interestingly, while the redox reaction of the polyselenide chains in 9a and 11 with S 8 produced 8 and [Se], the treatment of 8 with [Se] gave back only the starting material (8), thus demonstrating the different redox behavior of sulfur and selenium. Furthermore, the reaction of 8 and 9a/9b with activated alkynes and cyanide (CN − ) allowed the isolation of the complexes, [Co 2 (BPMP)(μ-E 2 C 2 (CO 2 R) 2 )] 1+ (E = S: 12a, R = Me; 12b, R = Et; E = Se: 13a, R = Me; 13b, R = Et) and [Co 2 (BPMP)(μ-SH)(NCS) 2 ] (14), respectively. The present work, thus, provides an interesting synthetic strategy, interconversions, and detailed comparative reactivity of binuclear Co(II)−polychalcogenido complexes.

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Computational refinement of the puzzling red tetrasulfur chromophore in ultramarine pigments

Rejmak

2020

Phys. Chem. Chem. Phys.

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Chemistry of Tetrasulfur Including Mysterious Rectangular S4 Metal Complexes

Cited by 3 publications

References 54 publications

Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

Generation and Reactivity of Polychalcogenide Chains in Binuclear Cobalt(II) Complexes

Computational refinement of the puzzling red tetrasulfur chromophore in ultramarine pigments

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