Electrocatalytic Hydrogen Production by an Aluminum(III) Complex: Ligand‐Based Proton and Electron Transfer

Thompson, Emily J.; Berben, Louise A.

doi:10.1002/ange.201503935

Cited by 43 publications

(13 citation statements)

References 50 publications

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“…5 For example, Berben et al showed that bis(imino)pyridine complex of aluminum catalyzed the dehydrogenative coupling of benzylamine, 6 dehydrogenation of formic acid, 7 and electrocatalytic production of hydrogen via a metal-ligand cooperative mechanism. 8 Roesky et al illustrated that the -diketiminato aluminum hydride complexes mediated the catalytic hydroboration of carbonyl compounds and alkynes. 9, 10 Thomas and Cowley et al reported that commercially available aluminum hydrides such as DIBAL-H and LiAlH 4 catalyzed the hydroboration of alkenes, alkynes, and nitriles via σ-bond metathesis.…”

Section: Introductionmentioning

confidence: 99%

Aluminum-Hydride-Catalyzed Hydroboration of Carbon Dioxide

et al. 2021

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This study describes the first use of a bis(phosphoranyl)methanido aluminum hydride, [ClC(PPh 2 NMes) 2 AlH 2 ] (2, Mes = Me 3 C 6 H 2 ) for the catalytic hydroboration of CO 2 . Complex 2 was synthesized by the reaction of a lithium carbenoid [Li(Cl)C(PPh 2 NMes) 2 ] with two equivalents of AlH 3 •NEtMe 2 in toluene at -78 o C. 10 mol % of 2 was able to catalyze the reduction of CO 2 with HBpin in C 6 D 6 at 110 o C for 2 days to afford a mixture of methoxyborane [MeOBpin] (3a; yield: 78 %, TOF: 0.16 h -1 ) and bis(boryl)oxide [pinBOBpin] (3b). When more potent [BH 3 •SMe 2 ] was used instead of HBpin, the catalytic reaction was extremely pure, resulting in the formation of trimethyl borate [B(OMe) 3 ] (3e) [catalytic loading: 1 mol % (10 mol %); reaction time: 60 min (5 min); yield: 97.6 % (>99 %); TOF: 292.8 h -1 (356.4 h -1 )] and B 2 O 3 (3f). Mechanistic studies show that the Al-H bond in complex 2 activated CO 2 to form [ClC(PPh 2 NMes) 2 Al(H){OC(O)H}] (4), which was subsequently reacted with BH 3 •SMe 2 to form 3e and 3f, along with the regeneration of complex 2. Complex 2 also shows good catalytic activity towards hydroboration of carbonyl, nitrile and alkyne derivatives. ASSOCIATED CONTENTSupporting Information. The Supporting Information is available free of charge on the ACS Publications website.Experimental procedures (PDF), theoretical studies (XYZ) X-ray crystallographic data (CIF)

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Section: Introductionmentioning

confidence: 99%

Aluminum-Hydride-Catalyzed Hydroboration of Carbon Dioxide

et al. 2021

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“…[33][34][35] Recently our group has reported a diorgano diselenide derived from the o-aminodiselenide ligand, which could activate aerial oxygen towards the oxidation of organothiols. [36][37] Inspired by nature 38 and by the non-transition metal electrocatalysts; zinc thiosemicarbazone and aluminium-bis aminopyridine (Scheme 1) for hydrogen evolution reactions (HER) from water, [30][31][39][40] herein, we report the synthesis and structural characterization of the novel bimetallic zinc selenolate electrocatalyst 1 that catalyzes the water-splitting reaction by ligand assisted pathways in both directions; oxygen evolution and hydrogen evolution reactions without adding acid or base. Mechanistic insights into the electrocatalytic activity of bimetallic zinc selenolate complex have also been gained by synthesizing mercury selenolate catalyst.…”

Section: Introductionmentioning

confidence: 99%

Water splitting into hydrogen and oxygen by non-traditional redox inactive zinc selenolate electrocatalyst

Upadhyay

Kumar

et al. 2020

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The development of alternative energy sources is the utmost priority of the developing society. Unlike many prior homogenous electrocatalysts that rely on the change in an oxidation state of metal center and or electrochemically active ligand, the synthesized novel bimetallic zinc selenolate complex consisting of redox inactive zinc metal ion and catalytically inactive ligand catalyzes the electrochemical oxygen evolution from the water with rate constant 7.28 s-1 at onset potential 1.028 V vs. NHE. On the other hand, the hydrogen evolution reaction proceeds with 47.32 s-1 observed rate constant and -0.256 V onset potential vs. NHE. DFT computations and control experiments suggest that the redox chemistry at selenium center, Lewis acidity, and cooperativity effect of two zinc atoms facilitate the electrochemical oxidation and reduction of water into oxygen and hydrogen, respectively.

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“…Umehara, Kuwata, and Ikariya demonstrated cleavage of the NN bond of hydrazines with an Fe pincer complex that relies on the ability of the ligand to undergo redox changes through multiple reversible protonation events 11. Thompson and Berben demonstrated the electrocatalytic production of dihydrogen by a ligand‐based protonation approach 12. Relatedly, Kirchner and co‐workers demonstrated the heterolytic cleavage of dihydrogen with an Fe‐NNN pincer complex 13.…”

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confidence: 99%