Exploring the role of pendant amines in transition metal complexes for the reduction of N2 to hydrazine and ammonia

Bhattacharya, Papri; Prokopchuk, Demyan E.; Mock, Michael T.

doi:10.1016/j.ccr.2016.07.005

Cited by 42 publications

(23 citation statements)

References 96 publications

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“…[308][309][310][311][312] Since the discovery of the first transition metal-dinitrogen complex ([Ru(N 2 ) (NH 3 ) 5 ] 2+ ) in 1965, 313 extensive efforts have been devoted to preparing a great number of well-defined transition metal dinitrogen complexes and examining the reactivity of coordinated N 2 ligand for the development of an efficient nitrogen fixation system working at ambient temperature and pressure. [314][315][316][317][318][319][320] In 2003, Yandulov 321 The yield of ammonia was 63% with TON = 4. 321 Since then, there have been extensive studies on the catalytic reduction of N 2 to NH 3 using Mo and Fe complexes.…”

Section: Production Of Ammonia and Hydrazine By Nitrogen Reductionmentioning

confidence: 99%

Production of Liquid Solar Fuels and Their Use in Fuel Cells

Fukuzumi

2017

Joule

175

116

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This review focuses on the production of liquid fuels using solar energy combined with their use in direct liquid fuel cells. The production of formic acid, which is the two-electron reduced product of CO 2 , as a solar liquid fuel as well as a hydrogen storage material is discussed together with its use in direct formate fuel cells. Other CO 2 reduction products such as methanol and formaldehyde as solar liquid fuels as well as hydrogen storage materials are reviewed with the performance of the corresponding fuel cells. The production of nitrogen fixation products such as ammonia and hydrazine is also reviewed together with their fuel cells. Finally, the production of hydrogen peroxide from not only pure water but also seawater and dioxygen in the air using solar energy is discussed and combined with the recent development of one-compartment hydrogen peroxide fuel cells.

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Section: Production Of Ammonia and Hydrazine By Nitrogen Reductionmentioning

confidence: 99%

Production of Liquid Solar Fuels and Their Use in Fuel Cells

Fukuzumi

2017

Joule

175

116

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“…Incorporation of ancillary aminecontaining ligands within transition-metal dinitrogen complexes has been previously explored by Mock and coworkers: they hypothesised that incorporation of pendant amines within the secondary coordination sphere could facilitate proton transfer towards the dinitrogen ligand. 29 Inclusion of a fixed amine site, such as in coordinated Ntriphos, could therefore offer different reactivity upon protonation.…”

Section: Acid Reactivity Of [Mo(n2)(dppm)(np3 Ph )] (2)mentioning

confidence: 99%

Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex

et al. 2018

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The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH2PPh2)3, NP3Ph) are reported. Reaction of N-triphos with [MoX3(THF)3] (X = Cl, Br, I) gave the Mo(iii) complex [MoX3(κ2-NP3Ph)(THF)] (1), where bidentate N-triphos coordination was observed. Reduction of this complex in the presence of dppm (bis(diphenylphosphino)methane) gave the dinitrogen complex [Mo(N2)(dppm)(κ3-NP3Ph)] (2), which exhibits moderate dinitrogen activation. An additional hydride complex, [Mo(H)2(dppm)(κ3-NP3Ph)] (4), was produced either as a minor side product during the reduction step, or as a major product by direct hydrogenation of the dinitrogen complex 2. The reactivity of the dinitrogen complex 2 with a range of Lewis acids was also investigated. At low temperatures, protic or borane Lewis acids (H+, BBr3 and tris(pentafluorophenyl)borane (BCF)) were found to coordinate to the apical nitrogen atom of the N-triphos ligand, with no conclusive evidence of any functionalisation of the dinitrogen ligand. Alkali metal Lewis acid addition to 2 resulted in the unexpected rearrangement of the N-triphos ligand to form [Mo(dppm)(PMePh2)(PCP)][B(C6F5)4] (7), where PCP, [Ph2PCNHCH2PPh2] is the carbenic ligand formed upon rearrangement from the reaction of 2 with M[B(C6F5)4] (M = Li, Na or K). Single crystal X-ray diffraction of complexes 1, 2, 4 and 7 provided structural confirmation of the N-triphos molybdenum complexes described.

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“…However, this concept has not been experimentally tested, which may be due to the synthetic challenges inherent in combining highly acidic and reducing centers in a single molecule. 6 Herein, we report an experimental test of the push–pull hypothesis through a systematic investigation of the ability of exogenous Lewis acids to activate a reduced Fe–N 2 complex.…”

Section: Introductionmentioning

confidence: 99%

Testing the Push–Pull Hypothesis: Lewis Acid Augmented N₂ Activation at Iron

2017

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We present a systematic investigation of the structural and electronic changes that occur in an Fe(0)–N2 unit (Fe(depe)2(N2); depe = 1,2-bis(diethylphosphino)-ethane) upon the addition of exogenous Lewis acids. Addition of neutral boranes, alkali metal cations, and an Fe2+ complex increases the N–N bond activation (Δ νNN up to 172 cm−1), decreases the Fe(0)–N2 redox potential, polarizes the N–N bond, and enables −N protonation at uncommonly anodic potentials. These effects were rationalized using combined experimental and theoretical studies.

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Exploring the role of pendant amines in transition metal complexes for the reduction of N2 to hydrazine and ammonia

Cited by 42 publications

References 96 publications

Production of Liquid Solar Fuels and Their Use in Fuel Cells

Production of Liquid Solar Fuels and Their Use in Fuel Cells

Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex

Testing the Push–Pull Hypothesis: Lewis Acid Augmented N₂ Activation at Iron

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Exploring the role of pendant amines in transition metal complexes for the reduction of N2 to hydrazine and ammonia

Cited by 42 publications

References 96 publications

Production of Liquid Solar Fuels and Their Use in Fuel Cells

Production of Liquid Solar Fuels and Their Use in Fuel Cells

Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex

Testing the Push–Pull Hypothesis: Lewis Acid Augmented N2 Activation at Iron

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Testing the Push–Pull Hypothesis: Lewis Acid Augmented N₂ Activation at Iron