2019
DOI: 10.1021/acs.inorgchem.8b02991
|View full text |Cite
|
Sign up to set email alerts
|

Synthetic Designs and Structural Investigations of Biomimetic Ni–Fe Thiolates

Abstract: Described are the syntheses of several Ni(μ-SR) 2 Fe complexes, including hydride derivatives, in a search for improved models for the active site of [NiFe]-hydrogenases. The nickel(II) precursors include (i) nickel with tripodal ligands: Ni(PS 3 ) − and Ni(NS 3 ) − (PS 3 3-= tris(phenyl-2thiolato)phosphine, NS 3 3-= tris(benzyl-2-thiolato)amine) (ii) traditional diphosphine-dithiolates, including chiral diphosphine R,R-DIPAMP, (iii) cationic Ni(phosphine-imine/amine) complexes,

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
5

Citation Types

1
16
0

Year Published

2021
2021
2024
2024

Publication Types

Select...
5
2
1

Relationship

1
7

Authors

Journals

citations
Cited by 19 publications
(17 citation statements)
references
References 92 publications
1
16
0
Order By: Relevance
“…(3) The mono-SPO mechanistic model proposed by previous studies could be suspicious due to lack of evidence. We suggested a new dual-phosphinito bridged Ni-Al complex (dual-SPO) to be an active catalyst shown in scheme 1c, which is quite similar to the structure of double thio-bridged nickel-iron hydrogenase in biological chemistry 41,42 . Further NMR study and computational study provided more evidences and applications for this novel model in this work.…”
Section: Introductionmentioning
confidence: 91%
“…(3) The mono-SPO mechanistic model proposed by previous studies could be suspicious due to lack of evidence. We suggested a new dual-phosphinito bridged Ni-Al complex (dual-SPO) to be an active catalyst shown in scheme 1c, which is quite similar to the structure of double thio-bridged nickel-iron hydrogenase in biological chemistry 41,42 . Further NMR study and computational study provided more evidences and applications for this novel model in this work.…”
Section: Introductionmentioning
confidence: 91%
“…Biocatalysts, such as [FeFe]-and [NiFe]-hydrogenases that efficiently and reversibly catalyze hydrogen evolution and oxidation in biological systems, encourage sciences to mimic their active sites. [5][6][7][8][9][10] Alternatively, noble metals such as platinum and palladium are always known as excellent catalysts for production and oxidation of hydrogen. However, bio-enzymes are difficult to adapt for the commercial applications, and the stability is often limited outside of the native environment, [11] as well as the scarcity and high cost of platinum and palladium limit the widespread application for hydrogen production.…”
Section: Introductionmentioning
confidence: 99%
“…[18] Because of the P S fragment in the thiophosphorylated calix [4]resorcinol ligand, the nickel atom is in a S 4 coordination sphere, leading to the nickel complexes can mimic the active sites of [NiFe]-hydrogenases, in which the nickel atom is also coordinated to four sulfur atoms. [7] The aminodiphosphine monosulfide as a hemilabile ligand continues to attract much attentions owing to the diversity in the coordination modes (mainly incorporate the P-monodentate and the hybrid P,S-chelate ligands). Furthermore, particularly, both the five-membered chelate ring and/or the P,P S donor set and the nature of the N-substituent influence the catalytic performances of the metal complexes.…”
Section: Introductionmentioning
confidence: 99%
“…[17][18][19] Further 1H + /1ereduction of the Ni-C state leads to the Ni-R state that releases H2 and regenerates the Ni-SIa state to complete the catalytic cycle. These Ni-L and Ni-C states of [NiFe] hydrogenases have been the inspiration for designing biomimetic catalysts for HER or HOR, 16,[20][21][22][23][24][25] however research efforts to utilize those catalysts in practical devices have had limited success. Furthermore, there are very few reports on the synthesis of complexes proposed to contain a Ni III -H species, 16,[26][27][28] Although recently molecular electrocatalysts bearing first-row transition metals such as nickel, [29][30][31][32] cobalt, [33][34][35] or iron [36][37][38] have gained significant recognition in the library of different catalysts for HER, the formation of H2 from 2H + and 2ewith high turnover under mild conditions is still challenging despite its thermodynamic simplicity.…”
Section: Introductionmentioning
confidence: 99%