Selenidobis(dithiolene)metal(IV) Complexes (Metal M = Mo, W) Potentially Related to the Nicotinic Acid Hydroxylase Reaction Center: Redox Aspects in Electrochemistry and Oxygen Atom Transfer from Me<sub>3</sub>NO to M<sup>IV</sup> Centers

Tano, Hiroyuki; Tajima, Reiko; Itoh, Shinobu; Sugimoto, Hideki

doi:10.1021/ic8009942

Cited by 21 publications

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“…The bis‐dithiolene complexes [M(CO) 2 (cydt) 2 ] {M = Mo: {MoCydt2} , M = W: {WCydt2} } as obtained by the nickel based trans‐metalation synthetic procedure are literature known but their respective crystal structures have not been published before , . We obtained these materials by the photochemical approach in as of yet unsatisfying yields but in high purity allowing the crystallization of the two complexes and their X‐ray structural investigation.…”

Section: Resultsmentioning

confidence: 99%

Photochemical Unmasking of 1,3‐Dithiol‐2‐ones: An Alternative Route to Heteroleptic Dithiolene Complexes from Low‐Valent Molybdenum and Tungsten Precursors

2019

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Mono-dithiolene complexes [Mo(CO) 2 (dt)(dppe)] and [W(CO) 2 (dt)(dppe)] {dt = cyclohex-1-ene-1,2-dithiol; 5,6-dihydro-2H-pyran-3,4-dithiol and dppe= 1,2-bis(diphenylphosphino)ethane} were synthesized by a photochemical procedure. The typical basic de-protection of the dithiolene ligand precursor was replaced by a light-induced opening of the 1,2-dithiole-2-one moiety. Advantages of this targeted approach comprise higher yields, cleaner transformations, and the possibility to continuously and precisely monitor the reaction progress. The [a] Scheme 1. Literature known pathways towards 1,2-dithiones and their tautomers: i. Nickel transfer metalation [7] ii. Chelotropic reaction of 1,3-dithiol-2ones initiated by UV-light [8] or heat [9] iii. Sulfuration of acetylenic compounds [10] iv. Sulfuration of dioxamides [11] v. Synthesis from thiirenes-1-oxides and Lawesson's Reagent. [12] tainly feasible approach towards metal-dithiolene complexes would be the direct use of 1,2-dithiones or their valence tautomers, [15] the 1,2-dithietes. This strategy was applied successfully to Pd, Ni, Co, Ru and Fe carbonyl precursors yielding bis-and trisdithiolene complexes. [15,16] With respect to the metals of our interest (Mo, W), in one case the reaction between the easily accessible bis(trifluoromethyl)-dithiete with hexacarbonyl molybdenum was described to yield 55 % of [Mo(S 2 C 4 F 6 ) 3 ]. [17] 1,2-Dithietes are commonly prepared by the reaction of elemental sulfur with the appropriate alkyne (Scheme 1; iii.) while not any alkyne leads to a wanted dithiete or dithione, though. [10,16b,18] The equilibrium between both tautomers is highly dependent on the backbone. Thus, electron-donating substituents usually stabilize dithiones [S 2 C 2 R 2 ; R = (p-dimethylamino)phenyl, 1-adamantyl] [8,19] while electron-withdrawing substituents favor dithietes which was established for the cases S 2 C 2 (CF 3 ) 2 , S 2 C 2 (CO 2 Me) 2 , and S 2 C 2 (CN) 2 . [9,20] Both, dithiones and dithietes are, however, undoubtedly unstable unless stabilized either electronically or sterically as they constitute reactive transient intermediates. [12] Comparably stable 1,2-dithiones are available from dioxamides upon thionation with Lawesson's Reagent (Scheme 1; iv.). [11] These specific species were first tested for the oxidative addition to molybdenum by Dieck and Form followed by only two related reports more than two decades later. [21] Electron donating dithiolenes which are not sterically hindered as for instance cyclic ones [e.g. cylohex-1-ene-1,2-dithiol (cydt) [22] or 5,6-dihydro-2H-pyran-3,4-dithiol (pydt) [23] ] or the well known S 2 C 2 Me 2 (mdt) [13] are neither isolable as dithiones/ dithietes nor as their unprotected alkali salts. Instead, precursors for this type of dithiolene ligand are commonly prepared in their 1,3-dithiol-2-one form. In order to coordinate such dithiolenes to metal carbonyl precursors their corresponding dithiones can be prepared in situ via a photochemically driven chelotropic decarbonylation (Scheme 1; ii.). ...

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Section: Resultsmentioning

confidence: 99%

Photochemical Unmasking of 1,3‐Dithiol‐2‐ones: An Alternative Route to Heteroleptic Dithiolene Complexes from Low‐Valent Molybdenum and Tungsten Precursors

2019

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“…18,19,20 In a similar manner, MoSL Ph and MoSeL Ph were synthesised. These two complexes, along with MoOL Ph , complete the second series of Mo IV E complexes including an identical ene-1,2-dithiolate ligand.…”

Section: Resultsmentioning

confidence: 99%

“…These observations indicate that the structure of the monomeric Mo(IV) species is unstable relative to one-electron oxidation processes. This instability likely results from dimerization, as both MoSL C4H8 and MoSeL C4H8 have been reported to yield dinuclear {[Mo V (L C4H8 ) 2 ] 2 (μ −S/Se) 2 } 2− structures upon one-electron oxidation, 19,20 and the UV–vis spectra of solutions obtained by chemical oxidation of MoSL Ph and MoSeL Ph with ferrocenium hexafluorophosphate are identical to those of dimeric {[Mo V (L Ph ) 2 ] 2 (μ − S/Se) 2 } 2− . 35 The MoSL COOMe and MoSeL COOMe complexes both exhibit an irreversible Mo(V)/Mo(IV) redox couple at E pa = −0.12 and −0.12 V, respectively, even with scan rates greater than 500 mV s −1 , indicating rapid dimerization of a putative square pyramidal Mo(V) species to generate {[Mo V (L COOMe ) 2 ] 2 (μ − S/Se) 2 } 2− .…”

Section: Resultsmentioning

confidence: 99%

“…All reactions were carried out under a dinitrogen atmosphere using standard Schlenk techniques. Complexes of MoOL C4H8 , 18 MoSL C4H8 , 19 MoSeL C4H8 , 20 MoOL Ph , 22 MoOL COOMe , 23 [Mo(CO) 2 (L Ph )] 24 and (Et 4 N)[Mo IV (OSitBuPh 2 )(L COOMe ) 2 ] ( Mo(OSitBuPh 2 )L COOMe ) 25 were prepared by following established literature procedures.…”

Section: Methodsmentioning

confidence: 99%

“…18–20 These complexes make possible detailed investigations regarding the effects of the MoE unit on the structure, spectroscopy and reactivity of the complexes. Regarding the square pyramidal structure, the active sites of reduced (i.e.…”

Section: Introductionmentioning

confidence: 99%

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Chalcogenidobis(ene-1,2-dithiolate)molybdenum(iv) complexes (chalcogenide E = O, S, Se): Probing MoE and ene-1,2-dithiolate substituent effects on geometric and electronic structure

et al. 2011

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New square–pyramidal bis(ene–1,2–dithiolate)MoSe complexes, [MoIVSe(L)2]2−, have been synthesised along with their terminal sulfido analogues, [MoIVS(L)2]2−, using alkyl (LC4H8), phenyl (LPh) and methyl carboxylate (LCOOMe) substituted dithiolene ligands (LR). These complexes now complete three sets of MoIVO, MoIVS and MoIVSe species that are coordinated with identical ene–1,2–dithiolate ligands. The alkyl substituted [Mo(S/Se)(LC4H8)2]2 − complexes were reported in prior investigations (H. Sugimoto, T. Sakurai, H. Miyake, K. Tanaka and H. Tsukube, Inorg. Chem. 2005, 44, 6927, H. Tano, R. Tajima, H. Miyake, S. Itoh and H. Sugimoto, Inorg. Chem. 2008, 47, 7465). The new series of complexes enable a systematic investigation of terminal chalcogenido and supporting ene–1,2–dithiolate ligand effects on geometric structure, electronic structure, and spectroscopic properties. X–ray crystallographic analysis of these (Et4N)2[Mo(E)L2] (E = terminal chalcogenide) complexes reveals an isostructural Mo centre that adopts a distorted square pyramidal geometry. The M≡E bond distances observed in the crystal structures and the ν(M≡E) vibrational frequencies indicate that these bonds are weakened with an increase in L→Mo electron donation (LCOOMe < LPh < LC4H8), and this order is confirmed by an electrochemical study of the complexes. The 77Se NMR resonances in MoSeL complexes appear at lower magnetic fields as the selenido ion became less basic from MoSeLC4H8, MoSeLPh and MoSeLCOOMe. Electronic absorption and resonance Raman spectroscopies have been used to assign key ligand-field, MLCT, LMCT and intraligand CT bands in complexes that possess the LCOOMe ligand. The presence of low-energy intraligand CT transition in these MoELCOOMe compounds directly probes the electron withdrawing nature of the −COOMe substituents, and this underscores the complex electronic structure of square pyramidal bis(ene–1,2–dithiolate)-MoIV complexes that possess extended dithiolene conjugation.

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Nitride‐Bridged Mo−Fe−S Double‐Cubanes: Syntheses, Redox Behaviors and Comparison with their W Analogs

Qiu,

Wei,

Zhang

et al. 2024

Eur J Inorg Chem

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The FeMo cofactor (FeMoco) of the Mo‐dependent nitrogenase was identified as a Mo‐Fe‐S cluster incorporating a 2p atom in the core. The edge‐bridged double‐cubane (EBDC, [M2Fe6(µ3‐S)6(µ4‐S)2]z (M = Mo/V; z denotes charge)) clusters were demonstrated to undergo rearrangement reactions to generate the apex‐fused double‐cubane clusters ([M2Fe6(μ2‐S)2(μ3‐S)6(μ6‐S)]z) as mimics of the PN‐clusters. The introduction of 2p atoms into the core of EBDC clusters will furnish the possibility of mimicking the FeMoco structure through rearrangement. In this work, an EBDC Mo‐Fe‐S cluster with core nitrides, namely [(Tp*)2Mo2Fe6(μ4‐N)2S6Cl4]2− (Tp* = tris(3,5‐dimethyl‐1‐pyrazolyl)hydroborate), has been synthesized. Subsequent terminal ligand substitution has produced a series of EBDC clusters with isostructural cores. Further studies of the series of nitride‐containing EBDC clusters are focused on their structures and redox properties, as well as comparisons with their W analogs. The results indicate that the core structures of these clusters are affected by distinct hetero‐metal centers and different terminal ligands to a limited extent, but the redox behavior and redox potentials of these clusters differ significantly. This work provides us with a viable method for regulating the properties of the nitride‐containing EBDC clusters, which may be enlightening for further studies of the rearrangement reactions towards mimicking the FeMoco structure.

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Selenidobis(dithiolene)metal(IV) Complexes (Metal M = Mo, W) Potentially Related to the Nicotinic Acid Hydroxylase Reaction Center: Redox Aspects in Electrochemistry and Oxygen Atom Transfer from Me₃NO to M^IV Centers

Cited by 21 publications

References 26 publications

Photochemical Unmasking of 1,3‐Dithiol‐2‐ones: An Alternative Route to Heteroleptic Dithiolene Complexes from Low‐Valent Molybdenum and Tungsten Precursors

Photochemical Unmasking of 1,3‐Dithiol‐2‐ones: An Alternative Route to Heteroleptic Dithiolene Complexes from Low‐Valent Molybdenum and Tungsten Precursors

Chalcogenidobis(ene-1,2-dithiolate)molybdenum(iv) complexes (chalcogenide E = O, S, Se): Probing MoE and ene-1,2-dithiolate substituent effects on geometric and electronic structure

Nitride‐Bridged Mo−Fe−S Double‐Cubanes: Syntheses, Redox Behaviors and Comparison with their W Analogs

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Selenidobis(dithiolene)metal(IV) Complexes (Metal M = Mo, W) Potentially Related to the Nicotinic Acid Hydroxylase Reaction Center: Redox Aspects in Electrochemistry and Oxygen Atom Transfer from Me3NO to MIV Centers

Cited by 21 publications

References 26 publications

Photochemical Unmasking of 1,3‐Dithiol‐2‐ones: An Alternative Route to Heteroleptic Dithiolene Complexes from Low‐Valent Molybdenum and Tungsten Precursors

Photochemical Unmasking of 1,3‐Dithiol‐2‐ones: An Alternative Route to Heteroleptic Dithiolene Complexes from Low‐Valent Molybdenum and Tungsten Precursors

Chalcogenidobis(ene-1,2-dithiolate)molybdenum(iv) complexes (chalcogenide E = O, S, Se): Probing MoE and ene-1,2-dithiolate substituent effects on geometric and electronic structure

Nitride‐Bridged Mo−Fe−S Double‐Cubanes: Syntheses, Redox Behaviors and Comparison with their W Analogs

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Selenidobis(dithiolene)metal(IV) Complexes (Metal M = Mo, W) Potentially Related to the Nicotinic Acid Hydroxylase Reaction Center: Redox Aspects in Electrochemistry and Oxygen Atom Transfer from Me₃NO to M^IV Centers