Synthesis, characterization and structural study of mercury(II) complexes with fluoroalkylthiocarbamates

Chniti, Ines; Sanhoury, M. A. K.; Maouati, Hamida; Guillot, Régis; Merlet, Denis; Chehidi, I.

doi:10.1016/j.molstruc.2016.08.055

Cited by 3 publications

(1 citation statement)

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“…The related thiocarbamate complex 6 , the product of a single cycloaddition of MesNCS to 1 , could only be accessed in a pure state when isolated as a precipitate after a brief reaction time in hexane. Thiocarbamate ligands, such as those found in 6 , are not commonly encountered in structurally characterized transition metal complexes. , The fact that 5 forms by a mechanism in which 6 is an intermediate supports the possibility that a terminal Re sulfide is generated by the ejection of isocyanate from 6 , which is then trapped by a second equivalent of MesNCS. Since a mixture of 5 and 6 was observed when only one equivalent of MesNCS was added to the reaction mixture, it appears that the ejection of isocyanate to form this putative terminal sulfide is relatively fast.…”

Section: Resultsmentioning

confidence: 98%

Diverse Reactivity of a Rhenium(V) Oxo Imido Complex: [2 + 2] Cycloadditions, Chalcogen Metathesis, Oxygen Atom Transfer, and Protic and Hydridic 1,2-Additions

et al. 2020

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We present a wide range of reactivity studies focused on the rhenium(V) oxo imido complex (DippN)(O)Re(BDI) (1, Dipp = 2,6-diisopropylphenyl and BDI = N,N′-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate). This complex, which was previously shown to possess a highly polarized Re oxo moiety, has proven to be a potent nucleophile and a valuable precursor to a variety of rare structural motifs in rhenium coordination complexes. For example, the Re oxo moiety of 1 undergoes [2 + 2] cycloadditions with carbodiimides, isocyanates, carbon dioxide, and isothiocyanates at room temperature. In the case of CO2, the cycloadduct with 1 (a carbonate complex) undergoes the facile ejection of CO2, demonstrating that this binding process is reversible. In the case of isothiocyanate, chalcogen metathesis with 1 takes place readily as the inclusion of a second equivalent of substrate in the reaction mixture rapidly yields a dithiocarbamate complex. This metathesis process was extended to the reactivity of 1 with phosphine chalcogenides, leading to the isolation of terminal sulfido imido and selenido imido complexes. Attempts to complete this series and generate the analogous terminal telluride led to the formation of a bidentate tritelluride (Te3 2–) complex. Triethylphosphine could only undergo oxygen atom transfer (OAT) with 1 under pressing thermal conditions that also led to C–N cleavage of the BDI ligand. In contrast, OAT between 1 and CO or 2,6-xylylisocyanide (XylNC) was found to be much more facile, proceeding within seconds at room temperature. While the addition of excess CO led to a rhenium(III) imido dicarbonyl complex, we found that the addition of 2 equiv of XylNC was necessary to promote OAT, resulting in the isolation of a rare example of a stable metal isocyanate complex. Our experimental observations of CO and XylNC and their OAT reactions with 1 inspired a mechanistic computational study to probe the intermediates and kinetic barriers along these reaction pathways. Finally, we describe 1,2-additions of both protic and hydridic substrates with the Re oxo moiety of 1, which most notably led to the syntheses of an uncommon example of a terminal rhenium hydroxide complex and an oxo-bridged Re–O–Zr hetero-bi-metallic complex that was generated using Schwartz’s reagent (Cp2ZrHCl). A brief discussion of a potential alternative route to 1 is also presented.

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Section: Resultsmentioning

confidence: 98%