1. A Metal–Organic Framework with Cooperative Phosphines That Permit Post‐Synthetic Installation of Open Metal Sites
- Author
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Joseph E. Reynolds, R. Eric Sikma, Alexander Steiner, Pranaw Kunal, Graeme Henkelman, Simon M. Humphrey, Samuel G. Dunning, Ji Sun Lee, Gianne Nandra, Jong-San Chang, Adam D Conn, and Wenrui Chai
- Subjects
Steric effects ,010405 organic chemistry ,chemistry.chemical_element ,General Chemistry ,General Medicine ,Heterogeneous catalysis ,010402 general chemistry ,Copper ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Metal ,chemistry.chemical_compound ,Crystallography ,chemistry ,visual_art ,visual_art.visual_art_medium ,Metal-organic framework ,Triphenylphosphine ,Phosphine - 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.
- Published
- 2018
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