Topic
Metalation
About: Metalation is a research topic. Over the lifetime, 4153 publications have been published within this topic receiving 98580 citations. The topic is also known as: metalation reaction.
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TL;DR: Several novel synthetic reactions of arenes and alkanes discovered and investigated in the laboratory are summarized here.
Abstract: Several novel synthetic reactions of arenes and alkanes discovered and investigated in our laboratory are summarized here. These include olefin arylation, hydroarylation of alkynes, hydroxylation of arenes, carboxylation of arenes and alkanes, and aminomethylation and acetoxylation of alkanes. Most of these reactions are catalyzed by highly electrophilic transition metal cationic species generated in situ in an acid medium, involving electrophilic metalation of C−H bonds of arenes and alkanes which lead to the formation of aryl−metal and alkyl−metal σ-complexes.
1,212 citations
TL;DR: A new synthetic strategy capable of metallating MOFs from the gas phase: atomic layer deposition (ALD) is introduced.
Abstract: Metal–organic frameworks (MOFs) have received attention for a myriad of potential applications including catalysis, gas storage, and gas separation. Coordinatively unsaturated metal ions often enable key functional behavior of these materials. Most commonly, MOFs have been metalated from the condensed phase (i.e., from solution). Here we introduce a new synthetic strategy capable of metallating MOFs from the gas phase: atomic layer deposition (ALD). Key to enabling metalation by ALD In MOFs (AIM) was the synthesis of NU-1000, a new, thermally stable, Zr-based MOF with spatially oriented −OH groups and large 1D mesopores and apertures.
737 citations
TL;DR: Efficient electrophilic metalation of aromatic C-H bonds leading to new C-C bond formation through regio- and stereoselective addition to alkynes and alkenes has been realized by a catalytic amount of palladium( II) or platinum(II) compounds in a mixed solvent containing trifluoroacetic acid at room temperature.
Abstract: Efficient electrophilic metalation of aromatic C-H bonds leading to new C-C bond formation through regio- and stereoselective addition to alkynes and alkenes has been realized by a catalytic amount (0.02 to 5 mole percent) of palladium(II) or platinum(II) compounds in a mixed solvent containing trifluoroacetic acid at room temperature. Various arenes undergo unexpected selective trans hydroarylation to terminal or internal CcC bonds inter- and intramolecularly with high efficiency (up to a turnover number of 4500 for palladium), especially for electron-rich arenes, giving thermodynamically unfavorable cis-alkenes, and the oxygen- and nitrogen-containing heterocycles. The simplicity, generality, and efficiency of this process should be very attractive to the possible industrial application for the functionalization of arenes.
731 citations
TL;DR: Two porphyrin-containing MOFs were metalated with iron(III) and copper(II) to yield the metalated analogues without losing their high surface area and chemical stability.
Abstract: Three new metal–organic frameworks [MOF-525, Zr6O4(OH)4(TCPP-H2)3; MOF-535, Zr6O4(OH)4(XF)3; MOF-545, Zr6O8(H2O)8(TCPP-H2)2, where porphyrin H4-TCPP-H2 = (C48H24O8N4) and cruciform H4-XF = (C42O8H22)] based on two new topologies, ftw and csq, have been synthesized and structurally characterized. MOF-525 and -535 are composed of Zr6O4(OH)4 cuboctahedral units linked by either porphyrin (MOF-525) or cruciform (MOF-535). Another zirconium-containing unit, Zr6O8(H2O)8, is linked by porphyrin to give the MOF-545 structure. The structure of MOF-525 was obtained by analysis of powder X-ray diffraction data. The structures of MOF-535 and -545 were resolved from synchrotron single-crystal data. MOF-525, -535, and -545 have Brunauer–Emmett–Teller surface areas of 2620, 1120, and 2260 m2/g, respectively. In addition to their large surface areas, both porphyrin-containing MOFs are exceptionally chemically stable, maintaining their structures under aqueous and organic conditions. MOF-525 and -545 were metalated with i...
705 citations
TL;DR: Solid state and solution evidence confirms the embedding of an adamantane-like, Ru4O6 fragment by the divacant, gamma-decatungstosilicate ligand in the resulting complex catalyzes water oxidation to oxygen with TON up to 500 and TOF > 450 h-1.
Abstract: Solid state and solution evidence confirms the embedding of an adamantane-like, Ru4O6 fragment by the divacant, γ-decatungstosilicate ligand. The resulting complex catalyzes water oxidation to oxygen with TON up to 500 and TOF > 450 h−1.
535 citations