A metal–organic framework-supported dinuclear iron catalyst for hydroboration of carbonyl compounds

Zhu, Yi-Jie; Wang, Junjie; Li, Junyu; Zhang, Teng

doi:10.1039/d3dt01109g

Cited by 5 publications

(2 citation statements)

References 63 publications

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“…In situ chemical reduction (primarily using NaHBEt 3 ) has been exploited to generate Co I , Co 0 , Ir I and Fe I sites (Figure 7). [10,59b,62] In 2016, Lin and co‐workers used post‐synthetic metalation to introduce Co II centres into UiO type MOFs bearing vacant bipyridine or phenanthroline N,N‐chelation sites [10] . The Co II centers were subsequently reduced to Co I using NaHBEt 3 in THF, forming a THF solvated Co I species with exceptional catalytic activity (Figure 7).…”

Section: Post‐synthetic Installation Of Low‐valent Metalsmentioning

confidence: 99%

“…Attempts to synthesise the analogous molecular catalyst were unsuccessful, instead furnishing [CoCl 2 (PPh 3 ) 2 ] which displayed significantly reduced activity towards C−H borylation. In 2023, the same strategy was extended to generate catalytically active single‐site low‐valent Fe moieties in a Zr IV MOF (Figure 7 c) [59b] …”

Section: Post‐synthetic Installation Of Low‐valent Metalsmentioning

confidence: 99%

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Low‐Valent Metals in Metal‐Organic Frameworks Via Post‐Synthetic Modification

Obeso,

Huxley,

de los Reyes

et al. 2023

Angewandte Chemie

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Metal‐organic frameworks (MOFs) provide uniquely tunable, periodic platforms for site‐isolation of reactive low‐valent metal complexes of relevance in modern catalysis, adsorptive applications, and for fundamental structural studies. Strategies for integrating such species in MOFs include, post‐synthetic metalation, encapsulation and direct synthesis using low‐valent organometallic complexes as building blocks. These approaches have each proven effective in enhancing catalytic activity, modulating product distributions (i.e., by improving catalytic selectivity), and by providing valuable mechanistic insights. In this minireview, we explore these different strategies, as applied to isolate low‐valent species within MOFs, with a particular focus on examples that leverage the unique crystallinity, permanent porosity and chemical mutability of MOFs, to achieve deep structural insights that lead to new paradigms in the field of hybrid catalysis.

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Section: Post‐synthetic Installation Of Low‐valent Metalsmentioning

confidence: 99%

Section: Post‐synthetic Installation Of Low‐valent Metalsmentioning

confidence: 99%

Low‐Valent Metals in Metal‐Organic Frameworks Via Post‐Synthetic Modification

Obeso,

Huxley,

de los Reyes

et al. 2023

Angewandte Chemie

View full text Add to dashboard Cite

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Low‐Valent Metals in Metal‐Organic Frameworks Via Post‐Synthetic Modification

Obeso,

Huxley,

de los Reyes

et al. 2023

Angew Chem Int Ed

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Multisite Amino‐Allylidene Ligands from Thermal CO Elimination in Diiron Complexes and Catalytic Activity in Hydroboration Reactions

Zappelli,

Taglieri,

Schoch

et al. 2024

ChemCatChem

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The new diiron(I) complexes [Fe2Cp2(μ‐CO){μ‐k3C,kN‐C(R1)C(R2)C(CN)NMe(R)}], 3a‐o (R = alkyl or 4‐C6H4OMe; R1 = alkyl, aryl, ferrocenyl (Fc), thiophenyl, CO2Me or SiMe3; R2 = H, Me or CO2Me) were synthesized in moderate to high yields from the thermal decarbonylation of the bis‐carbonyl precursors 2a‐o, and were structurally characterized by IR and NMR spectroscopy, and single crystal X‐ray diffraction in four cases. Electrochemical behavior of one complex was also investigated. Complexes 3a‐o comprise a highly functionalized, multisite amino‐(cyano)allylidene ligand, including metal coordination of a tertiary amine group. Selected complexes displayed negligible to moderate catalytic activity in CO2/propylene oxide coupling, working under ambient conditions. Additionally, they were investigated as catalysts for the conversion of benzaldehyde to the corresponding borate ester 6a, using pinacolborane (HBpin) as the borylating agent. Most complexes achieved good conversions at room temperature with 1% catalyst loading, and data highlight the significant influence of the multisite ligand substituents on the catalytic performance. Notably, complex 3m (featuring R = 4‐methoxyphenyl, R1 = Fc, R2 = H) displayed the highest activity and effectively catalyzed the hydroboration of various aldehydes and ketones. A plausible mechanistic cycle involves metal coordination of the carbonyl substrate, its activation being possibly facilitated by intramolecular interactions.

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A metal–organic framework-supported dinuclear iron catalyst for hydroboration of carbonyl compounds

Abstract: Preparation of catalytic active dinuclear transition metal complexes with open coordination sphere is a challenging task because the metal sites tend to be “saturated” with excess donor atoms around during...

Cited by 5 publications

References 63 publications

Low‐Valent Metals in Metal‐Organic Frameworks Via Post‐Synthetic Modification

Low‐Valent Metals in Metal‐Organic Frameworks Via Post‐Synthetic Modification

Low‐Valent Metals in Metal‐Organic Frameworks Via Post‐Synthetic Modification

Multisite Amino‐Allylidene Ligands from Thermal CO Elimination in Diiron Complexes and Catalytic Activity in Hydroboration Reactions

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