Insights from hydrogenase model studies on C–C bond forming reactions

Ogo, Seiji; Yatabe, Takeshi; Nakai, Hidetaka

doi:10.1016/j.ccr.2022.214697

Cited by 2 publications

(2 citation statements)

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“…Reductive elimination (RE) reactions are part of important catalytic processes. − RE with concomitant C–C cross-coupling plays a key role in the synthesis of organic molecules, including natural products and drugs. − RE from organometallic d 6 -configured octahedral Pt(IV) and Pd(IV) complexes with the concomitant formation of alkanes by Csp 3 –Csp 3 cross-coupling has been extensively studied, − while investigations on homo-coupling reactions are scarce. − …”

Section: Introductionmentioning

confidence: 99%

Cross-Coupling versus Homo-Coupling at a Pt(IV) Center: Computational and Experimental Approaches

et al. 2023

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C−C cross-coupling versus homo-coupling from the Pt(IV) complex [Pt(pbt)Br(CH 2 Ph)(Me) 2 ], 2a (pbt = 2-(2-pyridyl)benzothiazole), was studied experimentally and through density functional theory calculations. The calculations show that from the three competitive C−C reductive eliminations, (A) Me−Me homo-coupling, (B) benzyl−Me cross-coupling (Me trans to N py ), and (C) benzyl−Me cross-coupling (Me trans to N bz ), the Me−Me homo-coupling reaction is preferred over the other two due to the lower energy barrier of the Me−Me vs the benzyl−Me bond formation. The reaction is initiated by a dissociation of the Br − ligand followed by Me−Me homo-coupling from the resulting five-coordinate intermediate. Experimentally, complex 2a undergoes reductive elimination in toluene at 70 °C producing ethane and the Pt(II) complex [Pt(pbt)Br(CH 2 Ph)] 3a in over 99% yield, fully in line with the calculations. 1 H 195 Pt HMBC experiments allowed studying even sub-% products in this study.

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Section: Introductionmentioning

confidence: 99%

Cross-Coupling versus Homo-Coupling at a Pt(IV) Center: Computational and Experimental Approaches

et al. 2023

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“…Chemists have attempted to elucidate the mechanism of this hydrogen-mediated reduction to the low-valent species. [3][4][5][6][7][8][9] In pioneering work by DuBois and co-workers, a stepwise synthesis of Ni I complexes with planar ligands was demonstrated. First, Ni II complexes react with H 2 to give Ni 0 complexes.…”

Section: Introductionmentioning

confidence: 99%

Single‐Step Synthesis of Ni^I from Ni^II with H₂

Takahashi,

Yatabe,

Nakai

et al. 2023

Chemistry A European J

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Chemists have long sought to regulate the reactivity of H2, to yield hydride ions, hydrogen atoms, or electrons on demand. One source of inspiration for achieving this control is [NiFe]hydrogenase ([NiFe]H2ase), which reacts with H2 to form various hydrogen active species such as NiIII hydride species, NiII hydride species, and NiI low‐valent species. Chemists have attempted to synthesize these hydrogen active species not only as models for the active species of [NiFe]H2ase, but also as electron transfer catalysts. However, the synthesis of NiI complex directly from H2 has not been reported. This paper reports the first example of a single‐step synthesis of a NiI complex, via reaction of a NiII complex with H2, stable for over 3 months at room temperature and we further demonstrate a reductive coupling of acridinium ions as part of a reaction cycle.

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Insights from hydrogenase model studies on C–C bond forming reactions

Cited by 2 publications

References 59 publications

Cross-Coupling versus Homo-Coupling at a Pt(IV) Center: Computational and Experimental Approaches

Cross-Coupling versus Homo-Coupling at a Pt(IV) Center: Computational and Experimental Approaches

Single‐Step Synthesis of Ni^I from Ni^II with H₂

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Insights from hydrogenase model studies on C–C bond forming reactions

Cited by 2 publications

References 59 publications

Cross-Coupling versus Homo-Coupling at a Pt(IV) Center: Computational and Experimental Approaches

Cross-Coupling versus Homo-Coupling at a Pt(IV) Center: Computational and Experimental Approaches

Single‐Step Synthesis of NiI from NiII with H2

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Single‐Step Synthesis of Ni^I from Ni^II with H₂