CC Coupling of N‐Heterocycles at the <i>fac</i>‐Re(CO)<sub>3</sub> Fragment: Synthesis of Pyridylimidazole and Bipyridine Ligands

Espinal‐Viguri, Maialen; Pérez, Julio; Riera, Lucı́a

doi:10.1002/chem.201400155

Cited by 23 publications

(8 citation statements)

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“…10 [ReĲOMe 2 -bpy)ĲCO) 3 Cl] (0.06 g, 0.1 mmol) was converted to [ReĲOMe 2 -bpy)ĲCO) 3 ĲOTf)] by adding an excess of AgOTf (0.05 g, 0.2 mmol) in dichloromethane, and heating under reflux in the dark for c.a. 1 h. This known triflate species 42 was then isolated by filtration, purified by recrystallisation and its identity confirmed by NMR, IR and a comparison of its unit cell parameters by XRD. 1 3 ĲOTf)] (0.06 g, 0.1 mmol) was dissolved in 2 mL methanol and treated with an excess of KNO 2 (0.08 g, 1 mmol).…”

Section: Synthetic Proceduresmentioning

confidence: 99%

Understanding solid-state photoswitching in [Re(OMe₂-bpy)(CO)₃(η¹-NO₂)] crystals via in situ photocrystallography

Hatcher

2018

CrystEngComm

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Single-crystal-to-single-crystal nitro → nitrito isomerism is reported for the novel rheniumĲI)-bipyridine complex [ReĲOMe 2 -bpy)ĲCO) 3 Ĳη 1 -NO 2 )], achieving a maximum conversion of 66% to a photoinduced nitrito-(η 1 -O _NO) isomer under continuous illumination. The 3D X-ray structure of the photoinduced isomer is determined by steady-state and psuedo-steady-state photocrystallographic methods, providing insight into the structural changes required to accommodate photoswitching. Photocrystallographic kinetic studies follow the progress of photoswitching with time, determining a reaction rate constant of k = 0.38(2) min −1 at 150 K. Linkage isomerism is fully-reversible on warming, and pseudo-steady-state experiments confirm that the photoexcited state is retained, at measurable occupancy, up to a temperature of 240 K. These results confirm the validity of combining photoactive linkage isomer and ReĲI) photocatalyst chemistries, and the detailed determination of the photoexcited state structure will facilitate the future design of new photoactive ReĲI) crystals for a range of applications.5990 | CrystEngComm, 2018, 20, 5990-5997 This journal is Fig. 1 Single-crystal X-ray structure of the GS of 1 at 150 K. (a) Atomic connectivity in the asymmetric unit, ellipsoids at 50% probability, hydrogen atoms removed for clarity; (b) crystal packing arrangement; (c) C-H⋯O interactions involving the nitro-NO 2 ligand. CrystEngComm Paper

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Section: Synthetic Proceduresmentioning

confidence: 99%

Understanding solid-state photoswitching in [Re(OMe₂-bpy)(CO)₃(η¹-NO₂)] crystals via in situ photocrystallography

Hatcher

2018

CrystEngComm

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“…Rhenium tricarbonyldiimine complexes are an attractive class of electrocatalysts for probing the mechanistic pathways of reductive CO 2 activation owing to the wealth of literature precedent and their facile syntheses. − The canonical [Re(bpy)(CO) 3 Br] ( 0 , where bpy = 2, 2′-bipyridine; Scheme ), for instance, has been shown to reduce CO 2 to carbon monoxide (CO) with 100% selectivity over proton reduction. ,, A two-electron reduction of the rhenium(I) precursor yields a catalytically active anionic species that possesses a delocalized electron cloud and available π interactions from the equatorial carbonyl ligands, inducing the preferred formation of Re-CO 2 adducts over Re–H intermediates. , There is also a rich body of literature describing the in situ modification of redox-active unsaturated nitrogen-donor ligands under reducing or thermal conditions. ,− …”

Section: Introductionmentioning

confidence: 99%

Electrochemical Degradation of a Dicationic Rhenium Complex via Hoffman-Type Elimination

2021

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Electrocatalytic reduction of carbon dioxide (CO 2 ) by transition-metal catalysts is an attractive means for storing renewably sourced electricity in chemical bonds. Metal coordination compounds represent highly tunable platforms ideal for studying the fundamental stepwise transformations of CO 2 into its reduced products. However, metal complexes can decompose upon extended electrolysis and form chemically distinct molecular species or, in some cases, catalytically active electrode deposits. Deciphering the degradative pathways is important for understanding the nature of the active catalyst and designing robust metal complexes for small-molecule activation. Herein, we present a new dicationic rhenium bipyridyl complex capable of multielectron ligand-centered reductions electrochemically. Our in-depth experimental and computational study provides mechanistic insight into an unusual reductively induced Hoffman-type elimination. We identify benzylic tertiary ammonium groups as an electrolytically susceptible moiety and propose key intermediates in the degradative pathway. This investigation highlights the complex interplay between the ligand and metal ion and will guide the future design of metal−organic catalysts.

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“…formation of a new tridentate ligand by deprotonation of the central CH group of the imidazole, and further attack of the deprotonated N-coordinated imidazol-2-yl to the ortho CH group of the pyridyl ring (Scheme 14, above)[56]. The reaction occurs with dearomatization of the pyridyl group, now formally an anionic ligand, and it is selective, since the imidazole fragment of the pyridylimidazole chelate ligand remains unchanged.…”

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confidence: 99%

Re I (CO) 3 complexes with diimine ligands synthesized in situ

Villafañe

2017

Coordination Chemistry Reviews

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This work covers the coupling reactions of monodentate ligands coordinated to the "Re I (CO) 3 " moiety to afford in situ new bidentate diimine ligands. Similar reactions leading to tridentate ligands are also included. The reactions reviewed present evident advantages respect to the usual synthetic methods of these ligands. Besides, choosing the appropriate substituents allows an easy tuning of the properties of the final complexes. Following an approximate chronological order, the formation of bidentate ligands by C-N coupling from a coordinated carbonyl group, from diiminoisoindoline, and the formation of amidino ligands from nitriles are reviewed first. This is followed by the formation of bidentate ligands by C-C coupling, and finally by the formation of tridentate ligands, either by C-C coupling, by B-N coupling, or by using "click" reactions.

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CC Coupling of N‐Heterocycles at the fac‐Re(CO)₃ Fragment: Synthesis of Pyridylimidazole and Bipyridine Ligands

Cited by 23 publications

References 79 publications

Understanding solid-state photoswitching in [Re(OMe₂-bpy)(CO)₃(η¹-NO₂)] crystals via in situ photocrystallography

Understanding solid-state photoswitching in [Re(OMe₂-bpy)(CO)₃(η¹-NO₂)] crystals via in situ photocrystallography

Electrochemical Degradation of a Dicationic Rhenium Complex via Hoffman-Type Elimination

Re I (CO) 3 complexes with diimine ligands synthesized in situ

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CC Coupling of N‐Heterocycles at the fac‐Re(CO)3 Fragment: Synthesis of Pyridylimidazole and Bipyridine Ligands

Cited by 23 publications

References 79 publications

Understanding solid-state photoswitching in [Re(OMe2-bpy)(CO)3(η1-NO2)] crystals via in situ photocrystallography

Understanding solid-state photoswitching in [Re(OMe2-bpy)(CO)3(η1-NO2)] crystals via in situ photocrystallography

Electrochemical Degradation of a Dicationic Rhenium Complex via Hoffman-Type Elimination

Re I (CO) 3 complexes with diimine ligands synthesized in situ

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Product

Resources

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CC Coupling of N‐Heterocycles at the fac‐Re(CO)₃ Fragment: Synthesis of Pyridylimidazole and Bipyridine Ligands

Understanding solid-state photoswitching in [Re(OMe₂-bpy)(CO)₃(η¹-NO₂)] crystals via in situ photocrystallography

Understanding solid-state photoswitching in [Re(OMe₂-bpy)(CO)₃(η¹-NO₂)] crystals via in situ photocrystallography