Unexpected ligand effect on the catalytic reaction rate acceleration for hydrogen production using biomimetic nickel electrocatalysts with 1,5-diaza-3,7-diphosphacyclooctanes

Khrizanforova, Vera V.; Musina, Elvira I.; Khrizanforov, Mikhail; Gerasimova, Tatiana P.; Katsyuba, Sergey A.; Spiridonova, Yu. S.; Islamov, Daut R.; Kataeva, О. N.; Карасик, А. А.; Sinyashin, Оleg G.; Budnikova, Yulia H.

doi:10.1016/j.jorganchem.2015.04.044

Cited by 35 publications

(17 citation statements)

References 60 publications

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“…5 However novel ligands showed unpredicted properties like unique reversible slitting of macrocycles on to the smaller cycles, 18 rapid interconversion of isomers catalyzed by both acids and transitional metals, 21 bridging behavior of usually chelating ligands and an unexpectedly high influence of dangling substituents on N-atoms on to the catalytic and luminescent properties of P-complexes. 1,2,6,9,10 CONCLUSIONS Cyclic aminomethylphosphine ligands are powerful tools for design of transition metal complexes with predicted properties, however their ability for reversible transformations should be also taking into account.…”

Section: Resultsmentioning

confidence: 99%

Cyclic aminomethylphosphines as ligands: Balancing between rational design and unpredicted findings

Карасик

2016

Phosphorus, Sulfur, and Silicon and the Related Elements

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Rational design of title ligands led to the creation of high effective catalysts and perspective luminescent materials. However novel ligands showed unpredicted properties like spontaneous formation of macrocyclic molecules, unique reversible slitting of macrocycles on to the smaller cycles, rapid interconversion of the isomers catalyzed by both acids and transitional metals, bridging behavior of usually chelating ligands and the unexpected high influence of dangling substituents on N-atoms on to the catalytic and luminescent properties of P-complexes. GRAPHICAL ABSTRACT ACCEPTED MANUSCRIPT ACCEPTED MANUSCRIPT 2

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Section: Resultsmentioning

confidence: 99%

Cyclic aminomethylphosphines as ligands: Balancing between rational design and unpredicted findings

Карасик

2016

Phosphorus, Sulfur, and Silicon and the Related Elements

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“…> 200 • C (decomp. [(Cyclopentadienyl)carbonyl(3,7-di(pyridine-2 -yl)-1,5-di(p-tolyl)-1,5-diaza-3,7-diphosphacyclooctane)iron(II)] tetrafluoroborate (13). A solution of 4 (0.0656 g, 0.135 mmol) in dry toluene (5 mL) was added to solid [CpFe(CO) 2 (THF)]BF 4 (0.0456 g, 0.136 mmol) in dry toluene (1 mL).…”

Section: Electrochemical Measurementsmentioning

confidence: 99%

Synthesis and Structure of Iron (II) Complexes of Functionalized 1,5-Diaza-3,7-Diphosphacyclooctanes

et al. 2020

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In order to synthesize new iron (II) complexes of 1,5-diaza-3,7-diphosphacyclooctanes with a wider variety of the substituents on ligands heteroatoms (including functionalized ones, namely, pyridyl groups) and co-ligands, it was found that these ligands with relatively small phenyl, benzyl, and pyridin-2-yl substituents on phosphorus atoms in acetonitrile formed bis-P,P-chelate cis-complexes [L2Fe(CH3CN)2]2+ (BF4)2−, whereas P-mesityl-substituted ligand formed only monoligand P,P-complex [LFe(CH3CN)4]2+ (BF4)2−. 3,7-dibenzyl-1,5-di(1′-(R)-phenylethyl)-1,5-diaza-3,7-diphosphacyclooctane reacted with hexahydrate of iron (II) tetrafluoroborate in acetone to give an unusual bis-ligand cationic complex of the composition [L2Fe(BF4)]+ BF4−, where two fluorine atoms of the tetrafluoroborate unit occupied two pseudo-equatorial positions at roughly octahedral iron ion, according to X-ray diffraction data. 1,5-diaza-3,7-diphosphacyclooctanes replaced tetrahydrofurane and one of the carbonyl ligands of cyclopentadienyldicarbonyl(tetrahydrofuran)iron (II) tetrafluoroborate to form heteroligand complexes [CpFeL(CO)]+BF4−. The structural studies in the solid phase and in solutions showed that diazadiphosphacyclooctane ligands of all complexes adopted chair-boat conformations so that their nitrogen atoms were in close proximity to the central iron ion. The redox properties of the obtained complexes were performed by the cyclic voltammetry method.

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“…Electrochemical properties of complexes 1 (Ph‐Ph) and 2 (Ph‐Bn) in our experiments were studied by the method of solid‐phase electrochemistry (Table and Figure c,d). 1 (Ph‐Ph) in solid phase is characterized by two reversible reduction peaks (Figure c) corresponding to Ni (II) ↔ Ni (I) and Ni (I) ↔ Ni (0) transitions, whereas, in solution, the transitions are less cathodic on 50 mV. Complex 2 (Ph‐Bn) in the solid phase is also characterized by two reversible reduction peaks (Figure d) and corresponds to the Ni (II) ↔ Ni (I) and Ni (I) ↔ Ni (0) transitions.…”

Section: The Reduction Potentials Of the 1(ph‐ph) And 2(ph‐bn) Complexesmentioning

confidence: 99%

1,5‐Diaza‐3,7‐Diphosphacyclooctane Bis‐Ligand Nickel(II) Complexes as Oxygen Reduction Catalysts for Proton‐Exchange Membrane Fuel Cells

et al. 2019

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Membrane electrode assemblies (MEAs) with 1,5‐diaza‐3,7‐diphosphacyclootane organometallic bis‐ligand nickel(II) complexes [Ni(PPh2NPh2)2]2+2.[BF4]− [1(Ph‐Ph)] and [Ni(PPh2NBn2)2]2+2.[BF4]− [2(Ph‐Bn)] as a part of oxygen reduction reaction (ORR) catalysts for proton‐exchange membrane fuel cells (PEMFCs) are built and tested. The complexes are characterized by atomic force microscopy (AFM), electron spin resonance (ESR), cyclic voltammetry (CV), and differential scanning calorimetry‐thermogravimetric analysis (DSC‐TGA). Electrochemical activity toward ORR and catalytic stability of compounds is tested by chronoamperometry (CA). The electrochemical activity of catalysts and ORR mechanisms is studied by rotating disk electrode (RDE). A performance analysis of the PEMFC is carried out. A peak power density of about 11.84 mW cm−2 and a current density of 80 mA cm−2 are measured for 2(Ph‐Bn)/C cathode and Pt/C anode catalysts, respectively. Chronoamperometric tests in 0.5 m H2SO4 for 3 h show an excellent stability for the compound 2(Ph‐Bn). The performance of 1(Ph‐Ph)/C catalyst and the chronoamperometric stability of 1(Ph‐Ph) are worse. A possible relationship between the catalysts’ performance and basicity of pendant amines on the base of the proposed ORR mechanism with two metal centers is discussed.

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Unexpected ligand effect on the catalytic reaction rate acceleration for hydrogen production using biomimetic nickel electrocatalysts with 1,5-diaza-3,7-diphosphacyclooctanes

Cited by 35 publications

References 60 publications

Cyclic aminomethylphosphines as ligands: Balancing between rational design and unpredicted findings

Cyclic aminomethylphosphines as ligands: Balancing between rational design and unpredicted findings

Synthesis and Structure of Iron (II) Complexes of Functionalized 1,5-Diaza-3,7-Diphosphacyclooctanes

1,5‐Diaza‐3,7‐Diphosphacyclooctane Bis‐Ligand Nickel(II) Complexes as Oxygen Reduction Catalysts for Proton‐Exchange Membrane Fuel Cells

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