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

Autor: Dunning SG; Department of Chemistry, The University of Texas at Austin, 105 E 24th Street A5300, Welch Hall 2.204, Austin, TX, 78712-1224, USA., Nandra G; Department of Chemistry, The University of Texas at Austin, 105 E 24th Street A5300, Welch Hall 2.204, Austin, TX, 78712-1224, USA., Conn AD; Department of Chemistry, The University of Texas at Austin, 105 E 24th Street A5300, Welch Hall 2.204, Austin, TX, 78712-1224, USA., Chai W; Department of Chemistry, The University of Texas at Austin, 105 E 24th Street A5300, Welch Hall 2.204, Austin, TX, 78712-1224, USA., Sikma RE; Department of Chemistry, The University of Texas at Austin, 105 E 24th Street A5300, Welch Hall 2.204, Austin, TX, 78712-1224, USA., Lee JS; Research Center for Nanocatalysts, Korea Research Institute of Chemical Technology, P.O. Box 107, Yusung, Daejeon, 305-600, Korea., Kunal P; Department of Chemistry, The University of Texas at Austin, 105 E 24th Street A5300, Welch Hall 2.204, Austin, TX, 78712-1224, USA., Reynolds JE 3rd; Department of Chemistry, The University of Texas at Austin, 105 E 24th Street A5300, Welch Hall 2.204, Austin, TX, 78712-1224, USA., Chang JS; Research Center for Nanocatalysts, Korea Research Institute of Chemical Technology, P.O. Box 107, Yusung, Daejeon, 305-600, Korea.; Department of Chemistry, Sungkyunkwan University, Suwon, 440-476, Korea., Steiner A; Department of Chemistry, University of Liverpool, Crown St., Liverpool, L69 7ZD, UK., Henkelman G; Department of Chemistry, The University of Texas at Austin, 105 E 24th Street A5300, Welch Hall 2.204, Austin, TX, 78712-1224, USA., Humphrey SM; Department of Chemistry, The University of Texas at Austin, 105 E 24th Street A5300, Welch Hall 2.204, Austin, TX, 78712-1224, USA.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2018 Jul 20; Vol. 57 (30), pp. 9295-9299. Date of Electronic Publication: 2018 Jun 25.
DOI: 10.1002/anie.201802402
Abstrakt: PCM-101 is a phosphine coordination material comprised of tris(p-carboxylato)triphenylphosphine and secondary pillaring groups coordinated to [M 3 (OH)] 5+ nodes (M=Co, Ni). PCM-101 has a unique topology in which R 3 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.
(© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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