Synthesis, characterization and crystal structure of rhenium(I) tricarbonyl diimine complexes coupled with their efficiency in producing hydrogen in a photocatalytic system

Kefalidi, Christina; Koutsouri, Eugenia; Marchiò, Luciano; Ζαρκαδούλας, Αθανάσιος; Efstathiadou, Sofia; Mitsopoulou, Christiana A.

doi:10.1016/j.poly.2016.02.043

Cited by 14 publications

(34 citation statements)

References 54 publications

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“…This can be attributed to the difference in the nature of the diimine ligands which reflects on the electronic properties of the complexes, following the series bpy > amphen > pq. This rate reproduces results we reported earlier, where cobaloximes were used as reductive catalysts,[3a] indicating that diimine ligand is of the same importance for this class of photosensitizers. Moreover, this can be attributed to the influence of the diimine ligand on the photosensitizer's lifetime [ReBr(CO) 3 (bpy)] (PS1) ( τ re = 51 ns at 25 °C)[2b] and [ReBr(CO) 3 (amphen)] (PS4) ( τ re = 4.2 ± 0.1 ns at 25 °C) and as a consequence the most long‐lived [ReBr(CO) 3 (bpy)] (PS1) can react effectively with the TEOA and advance the overall catalytic cycle.…”

Section: Resultssupporting

confidence: 91%

“…. According to the literature, responsible for this process are the remaining protons from water and the decomposition of TEOA[3a], [14b] (Figure ) whereas the drawback of the acetic acid has been attributed to its interaction with the PS. The latter is proportional to the increase of the [AcOH].…”

Section: Resultsmentioning

confidence: 99%

“…It is well documented that photosystems with [ReL(CO) 3 (NN)] 0/+ as PS, cobaloximes as catalysts and TEOA[14b] in DMF proceed towards hydrogen production through a reductive quenching pathway, which means that photoexcitation of the photosensitizer results to [ReL(CO) 3 (NN)] * followed by quenching by TEOA to produce [ReL(CO) 3 (NN)] – which consequently reduces the catalyst. [2b], Based on these previous results and using the literature values for the excited state lifetime of [ReBr(CO) 3 (bpy)] (PS1) ( τ re = 51 ns at 25 °C)[2b] and [ReBr(CO) 3 (amphen)] (PS4) ( τ re = 4.2 ± 0.1 ns at 25 °C),[3a], we performed a series of excited state quenching experiments for our systems.…”

Section: Resultsmentioning

confidence: 99%

“…[ReBr(CO) 3 (amphen)] (PS4): The complex [ReBr(CO) 3 (amphen)]was synthesized according to literature procedures. [3a], , [46b] Yield: 85.46 %. 1 H NMR (300 MHz, [D 6 ]DMSO, δ ppm), 9.39 (d, 1H), 9.09 (d, 1H), 8.95 (d, 1H), 8.46 (d, 1H), 8.05 (t, 1H), 7.79 (t, 1H), 7.07 (s, 1H), 6.89 (s, 2H, NH 2 ).…”

Section: Methodsmentioning

confidence: 99%

“…[ReBr(CO) 3 (pq)] (PS5): For the synthesis of complex [ReBr(CO) 3 (pq)]a literature procedure was followed. [3a], Yield: 62 %. 1 H NMR (300 MHz, [D 6 ]DMSO0 δ ppm), 10.22 (s, 1H), 9.26 (d, 1H), 9.17 (d, 1H), 8.67 (d, 1H), 8.47 (t, 1H), 8.36 (d, 1H), 8.24 (t, 1H), 8.13 (d, 1H), 7.90 (t, 1H).…”

Section: Methodsmentioning

confidence: 99%

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Establishing Structure–Activity Relationships in Photocatalytic Systems by Using Nickel Bis(dithiolene) Complexes as Proton Reduction Catalysts

et al. 2019

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Herein, we present an artificial photocatalytic system for H2 evolution based on a series of proton reduction catalysts, namely [Ni{S2C2(Ph)2}2] (1), [Ni{S2C2(Ph)2}2](NEt4) (1–), [Ni{S2C2(Ph)(Ph–OCH3‐4)}2] (2), [Ni{S2C2(Ph)(Ph–OCH3‐4)}2](NEt4) (2–), [Ni{S2C2(Ph–OCH3‐4)2}2] (3) and [Ni{S2C2(Ph–OCH3‐4)2}2](NEt4) (3–), [Ni(mnt)2] (NBu4) (4–), [Ni(mnt)(S2C2(Ph)2)](NBu4) (5–). These complexes are different of both in charge and the substituents on dithiolene ligand and represent a group of active catalysts for the reduction of protons with high TONs. A series of ReI complexes, [ReBr(CO)3 (bpy)], [ReCl(CO)3(bpy)], [Re(NCS)(CO3)(bpy)], [ReBr(CO)3(amphen)] and [ReBr(CO)3 (pq)] were used as photosensitizers, in combination with triethanolamine as a sacrificial electron donor and acetic acid as a proton source. The differences of the ligands in the electron donating properties and reactivity are discussed in the light of the experimental data. We also present the physicochemical characterization of a previously reported heteroleptic monoanionic complex (5–), by UV/Vis spectroscopy, FTIR spectroscopy, cyclic voltammetry and single‐crystal X‐ray diffraction studies.

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Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Establishing Structure–Activity Relationships in Photocatalytic Systems by Using Nickel Bis(dithiolene) Complexes as Proton Reduction Catalysts

et al. 2019

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Addition of Re‐Bonded Nucleophilic Ligands to Activated Alkynes: A Theoretical Rationalization

et al. 2020

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Reactions between [Re(X)(CO)3(bipy)] (X = OH, OMe, NHpTol, PPh2; bipy = 2,2'-bipyridine) complexes and methyl propiolate (HMAD) are studied to rationalize the different products experimentally obtained. Three reaction patterns were found with a common and limiting initial attack of X to HMAD. Thus, the experimental selectivity depends on the kinetics and/or thermodynamics of the last reaction stages. For X = OH and NHpTol an easy intramolecular attack of the X-linked HMAD to a highly electrophilic CO ligand is followed by a hydrogen transposition to this CO, yielding very stable species (C-CCOH products). When X = OMe, the insertion of the X-attached HMAD into the Re-OMe bond (ins product) takes place due to the smallest barrier and the largest stability of the ins route. Finally, when X = PPh2 the ins route becomes restricted and the route for the coupling of the X-attached HMAD with bipy (C-Cbipy product) wins over the one for the coupling with CO (C-CCO product) only due to the larger stability of the C-Cbipy product.

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Alkyl 2-benzothiazolyl sulfide ligated dirhenium complexes: Syntheses, structure and computational study of [Re2(CO)8{μ,κ1,κ1–(R)SCNC6H4S}] (R = CH3 and C2H5)

et al. 2021

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Synthesis, characterization and crystal structure of rhenium(I) tricarbonyl diimine complexes coupled with their efficiency in producing hydrogen in a photocatalytic system

Cited by 14 publications

References 54 publications

Establishing Structure–Activity Relationships in Photocatalytic Systems by Using Nickel Bis(dithiolene) Complexes as Proton Reduction Catalysts

Establishing Structure–Activity Relationships in Photocatalytic Systems by Using Nickel Bis(dithiolene) Complexes as Proton Reduction Catalysts

Addition of Re‐Bonded Nucleophilic Ligands to Activated Alkynes: A Theoretical Rationalization

Alkyl 2-benzothiazolyl sulfide ligated dirhenium complexes: Syntheses, structure and computational study of [Re2(CO)8{μ,κ1,κ1–(R)SCNC6H4S}] (R = CH3 and C2H5)

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