A Metal-Organic Framework with Cooperative Phosphines That Permit Post-Synthetic Installation of Open Metal Sites

Angewandte Chemie
Samuel G DunningSimon M Humphrey

Abstract

PCM-101 is a phosphine coordination material comprised of tris(p-carboxylato)triphenylphosphine and secondary pillaring groups coordinated to [M3 (OH)]5+ nodes (M=Co, Ni). PCM-101 has a unique topology in which R3 P: sites are arranged directly trans to one another, with a P⋅⋅⋅P separation distance dictated by the pillars. Post-synthetic coordination of soft metals to the P: sites proceeds at room temperature to provide X-ray quality crystals that permit full structural resolution. Addition of AuCl groups forces a large distortion of the parent framework. In contrast, CuBr undergoes insertion directly between the trans-P sites to form dimers that mimic solution-phase complexes, but that are geometrically strained due to steric pressure exerted by the MOF scaffold. The metalated materials are active in heterogeneous hydroaddition catalysis under mild conditions, yielding different major products compared to their molecular counterparts.

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Citations

Aug 18, 2018·Chemical Communications : Chem Comm·Joseph E ReynoldsSimon M Humphrey
Sep 21, 2018·Chemical Society Reviews·Angelo KirchonHong-Cai Zhou
Aug 2, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Qingqing PangQiaowei Li
May 13, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Jing ChenDavid J Young
Aug 25, 2020·ChemPlusChem·Ben S Pilgrim, Neil R Champness
Feb 20, 2021·Chemical Society Reviews·Georgia R F OrtonNeil R Champness
Aug 20, 2021·Journal of the American Chemical Society·R Eric SikmaSimon M Humphrey
Jul 22, 2018·Journal of the American Chemical Society·R Eric SikmaSimon M Humphrey
Jul 12, 2020·Journal of the American Chemical Society·Ricardo A PeraltaChristian J Doonan
May 2, 2020·Chemical Reviews·Yong-Sheng WeiQiang Xu
Mar 29, 2020·ACS Applied Materials & Interfaces·Shengxian ChengZhengtao Xu

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