Synthesis and characterization of asymmetric [Mo2O2(μ-S)2(S2)(L)] complexes (L = bipy, en, dien) and their heterogeneous reaction with propylene sulfide

Birgisson, Benedikt Orri; Monger, Lindsey J.; Damodaran, Krishna K.; Suman, Sigridur G.

doi:10.1016/j.ica.2019.119272

Cited by 7 publications

(12 citation statements)

References 54 publications

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“…They are representative of the spectra of the mono- and bis-α-amino acid complexes shown with the same amino acid ligand. The electronic spectrum of 4 exhibits a charge transfer band (π)S → (d)Mo of the four-membered ring “Mo 2 S 2 ” with a maximum at 274 nm and shoulders at 305 and 347 nm from d–d transitions of the central metals, which are consistent with previous reports. ,, …”

Section: Resultssupporting

confidence: 78%

“…A weak absorbance at 474 nm was observed that was is associated with n−π* transition in the disulfide ligand . This absorbance is absent in the spectrum of 8 , as expected.…”

Section: Resultsmentioning

confidence: 99%

“…The fact that the bis - amino acid complexes 7 and 8 show higher water solubilities than their corresponding disulfide potassium salts suggests that the incorporation of highly water-soluble ligands plays a more significant role in increasing the water solubility than adding a water-soluble countercation. Strong intermolecular S···S interactions can negatively impact the solubility of compounds with the “Mo 2 O 2 (μ-S) 2 (S 2 )” moiety, where the disulfide sulfur atoms may interact with a bridging sulfur atom in another molecule . Complexes 2 and 6 are therefore likely to have comparably low solubilities.…”

Section: Resultsmentioning

confidence: 99%

“…The electronic spectrum of 4 exhibits a charge transfer band (π)S → (d)Mo of the four-membered ring "Mo 2 S 2 " with a maximum at 274 nm and shoulders at 305 and 347 nm from d−d transitions of the central metals, which are consistent with previous reports. 47,49,69 A weak absorbance at 474 nm was observed that was is associated with n−π* transition in the disulfide ligand. 69 This absorbance is absent in the spectrum of 8, as expected.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…47,49,69 A weak absorbance at 474 nm was observed that was is associated with n−π* transition in the disulfide ligand. 69 This absorbance is absent in the spectrum of 8, as expected. The electronic spectrum of 8 exhibits a charge-transfer band with a maximum at 281 and a shoulder at 350, which are analogous to the bands observed for 4.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Water-Soluble α-Amino Acid Complexes of Molybdenum as Potential Antidotes for Cyanide Poisoning: Synthesis and Catalytic Studies of Threonine, Methionine, Serine, and Leucine Complexes

et al. 2020

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Water-soluble complexes are desirable for the aqueous detoxification of cyanide. Molybdenum complexes with α-amino acid and disulfide ligands with the formula K[(L)Mo2O2(μ-S)2(S2)] (L = leu (1), met (2), thr (3), and ser (4)) were synthesized in a reaction of [(DMF)3MoO(μ-S)2(S2)] with deprotonated α-amino acids; leu, met, thr, and ser are the carboxylate anions of l-leucine, l-methionine, l-threonine, and l-serine, respectively. Potassium salts of α-amino acids (leu (1a), met (2a), thr (3a), and ser (4a)) were prepared as precursors for complexes 1–4, respectively, by employing a nonaqueous synthesis route. The ligand exchange reaction of [Mo2O2(μ-S)2(DMF)6](I)2 with deprotonated α-amino acids afforded bis-α-amino acid complexes, [(L)2Mo2O2(μ-S)2] (6–8). A tris-α-amino acid complex, [(leu)2Mo2O2(μ-S)2(μ-leu + H)] (5; leu + H is the carboxylate anion of l-leucine with the amine protonated), formed in the reaction with leucine. 5 crystallized from methanol with a third weakly bonded leucine as a bridging bidentate carboxylate. An adduct of 8 with SCN coordinated, 9, crystallized and was structurally characterized. Complexes 1–4 are air stable and highly water-soluble chiral molecules. Cytotoxicity studies in the A549 cell line gave IC50 values that range from 80 to 400 μM. Cyclic voltammetry traces of 1–8 show solvent-dependent irreversible electrochemical behavior. Complexes 1–4 demonstrated the ability to catalyze the reaction of thiosulfate and cyanide in vitro to exhaustively transform cyanide to thiocyanate in less than 1 h.

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Section: Resultssupporting

confidence: 78%

“…A weak absorbance at 474 nm was observed that was is associated with n−π* transition in the disulfide ligand . This absorbance is absent in the spectrum of 8 , as expected.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

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Water-Soluble α-Amino Acid Complexes of Molybdenum as Potential Antidotes for Cyanide Poisoning: Synthesis and Catalytic Studies of Threonine, Methionine, Serine, and Leucine Complexes

et al. 2020

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Thiomolybdate Clusters: From Homogeneous Catalysis to Heterogenization and Active Sites

Batool,

Langer,

Myakala

et al. 2023

Advanced Materials

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Thiomolybdates are molecular molybdenum‐sulfide clusters formed from Mo centers and sulfur‐based ligands. For decades, they have attracted the interest of synthetic chemists due to their unique structures and their relevance in biological systems, e.g., as reactive sites in enzymes. More recently, thiomolybdates have been explored from the catalytic point of view and applied as homogeneous and molecular mimics of heterogeneous molybdenum sulfide catalysts. This review summarizes prominent examples of thiomolybdate‐based electro‐ and photocatalysis and provides a comprehensive analysis of their reactivities under homogeneous and heterogenized conditions. Active sites of thiomolybdates relevant for the hydrogen evolution reaction (HER) are examined, aiming to shed light on the link between cluster structure and performance. The shift from solution‐phase to surface‐supported thiomolybdates is discussed with a focus on applications in electrocatalysis and photocatalysis. The outlook highlights current trends and emerging areas of thiomolybdate research, ending with a summary of challenges and key takeaway messages based on the state‐of‐the‐art research.This article is protected by copyright. All rights reserved

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Protonation and Sulfidation of [(Me₃tacn)MO₃] (M=Mo, W)

Cheng

Qian

et al. 2022

ChemistrySelect

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Protonation of [(Me3tacn)MoO3] with one or two equivalents of strong proton acid afforded mono‐protonated complex [(Me3tacn)MoVIO2(OH)](CF3SO3) and bi‐protonated complex [(Me3tacn)MoVIO(OH)2](PF6)2, respectively. Sulfidation with iPr2NCS2Na or CS2 in acetonitrile, followed by in situ protonation of [(Me3tacn)MO3] (M=Mo, W), produced two monomeric complexes [(Me3tacn)MoVIO2S] ⋅ (iPr2NH2) ⋅ (PF6) ⋅ CH2Cl2 and [(Me3tacn)WVIO2S], and two dimeric complexes [(Me3tacn)MoVO(μ‐S)2MoVO(κ2‐S2C=O)] ⋅ CH3CN and [(Me3tacn)MoIVO]2(μ‐O)(μ‐S2) ⋅ 2DMF. The crystal structures of the two protonated molybdenum(VI) complexes and the four oxo‐sulfido molybdenum/tungsten complexes have been determined. Moreover, the complexes have been characterized by infrared, Raman, fluorescence and UV‐vis spectroscopies. (Me3tacn=1,4,7‐trimethyl‐1,4,7‐triazacyclonane).

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Synthesis and characterization of asymmetric [Mo2O2(μ-S)2(S2)(L)] complexes (L = bipy, en, dien) and their heterogeneous reaction with propylene sulfide

Cited by 7 publications

References 54 publications

Water-Soluble α-Amino Acid Complexes of Molybdenum as Potential Antidotes for Cyanide Poisoning: Synthesis and Catalytic Studies of Threonine, Methionine, Serine, and Leucine Complexes

Water-Soluble α-Amino Acid Complexes of Molybdenum as Potential Antidotes for Cyanide Poisoning: Synthesis and Catalytic Studies of Threonine, Methionine, Serine, and Leucine Complexes

Thiomolybdate Clusters: From Homogeneous Catalysis to Heterogenization and Active Sites

Protonation and Sulfidation of [(Me₃tacn)MO₃] (M=Mo, W)

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Synthesis and characterization of asymmetric [Mo2O2(μ-S)2(S2)(L)] complexes (L = bipy, en, dien) and their heterogeneous reaction with propylene sulfide

Cited by 7 publications

References 54 publications

Water-Soluble α-Amino Acid Complexes of Molybdenum as Potential Antidotes for Cyanide Poisoning: Synthesis and Catalytic Studies of Threonine, Methionine, Serine, and Leucine Complexes

Water-Soluble α-Amino Acid Complexes of Molybdenum as Potential Antidotes for Cyanide Poisoning: Synthesis and Catalytic Studies of Threonine, Methionine, Serine, and Leucine Complexes

Thiomolybdate Clusters: From Homogeneous Catalysis to Heterogenization and Active Sites

Protonation and Sulfidation of [(Me3tacn)MO3] (M=Mo, W)

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Synthesis and characterization of asymmetric [Mo2O2(μ-S)2(S2)(L)] complexes (L = bipy, en, dien) and their heterogeneous reaction with propylene sulfide

Protonation and Sulfidation of [(Me₃tacn)MO₃] (M=Mo, W)