Trivalent Zirconium and Hafnium Metal-Organic Frameworks for Catalytic 1,4-Dearomative Additions of Pyridines and Quinolines.

Title Trivalent Zirconium and Hafnium Metal-Organic Frameworks for Catalytic 1,4-Dearomative Additions of Pyridines and Quinolines.
Authors P. Ji; X. Feng; S.S. Veroneau; Y. Song; W. Lin
Journal J Am Chem Soc
DOI 10.1021/jacs.7b09093
Abstract

We report the quantitative conversion of [MIV6(?3-O)4(?3-OH)4Cl12]6- nodes in the MCl2-BTC metal-organic framework into the [MIII6(?3-O)4(?3-ONa)4H6]6- nodes in MIIIH-BTC (M = Zr, Hf; BTC is 1,3,5-benzenetricarboxylate) via bimetallic reductive elimination of H2 from putative [MIV6(?3-O)4(?3-OH)4H12]6- nodes. The coordinatively unsaturated MIIIH centers in MIIIH-BTC are highly active and selective for 1,4-dearomative hydroboration and hydrosilylation of pyridines and quinolines. This work demonstrated the potential of secondary building unit transformation in generating electronically unique and homogeneously inaccessible single-site solid catalysts for organic synthesis.

Citation P. Ji; X. Feng; S.S. Veroneau; Y. Song; W. Lin.Trivalent Zirconium and Hafnium Metal-Organic Frameworks for Catalytic 1,4-Dearomative Additions of Pyridines and Quinolines.. J Am Chem Soc. 2017;139(44):1560015603. doi:10.1021/jacs.7b09093

Related Elements

Hafnium

See more Hafnium products. Hafnium (atomic symbol: Hf, atomic number: 72) is a Block D, Group 4, Period 6 element with an atomic weight of 178.49. Hafnium Bohr ModelThe number of electrons in each of Hafnium's shells is 2, 8, 18, 32, 10, 2 and its electron configuration is [Xe] 4f14 5d2 6s2. The hafnium atom has a radius of 159 pm and a Van der Waals radius of 212 pm. Hafnium was predicted by Dmitri Mendeleev in 1869 but it was not until 1922 that it was first isolated Dirk Coster and George de Hevesy. In its elemental form, hafnium has a lustrous silvery-gray appearance. Elemental HafniumHafnium does not exist as a free element in nature. It is found in zirconium compounds such as zircon. Hafnium is often a component of superalloys and circuits used in semiconductor device fabrication. Its name is derived from the Latin word Hafnia, meaning Copenhagen, where it was discovered.

Zirconium

See more Zirconium products. Zirconium (atomic symbol: Zr, atomic number: 40) is a Block D, Group 4, Period 5 element with an atomic weight of 91.224. Zirconium Bohr ModelThe number of electrons in each of Zirconium's shells is 2, 8, 18, 10, 2 and its electron configuration is [Kr]4d2 5s2. The zirconium atom has a radius of 160 pm and a Van der Waals radius of 186 pm. Zirconium was discovered by Martin Heinrich Klaproth in 1789 and first isolated by Jöns Jakob Berzelius in 1824. In its elemental form, zirconium has a silvery white appearance that is similar to titanium. Zirconium's principal mineral is zircon (zirconium silicate). Elemental ZirconiumZirconium is commercially produced as a byproduct of titanium and tin mining and has many applications as a opacifier and a refractory material. It is not found in nature as a free element. The name of zirconium comes from the mineral zircon, the most important source of zirconium, and from the Persian wordzargun, meaning gold-like.

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