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Abstract Metal–organic frameworks (MOFs) constructed with M0nodes are attractive targets due to the reactivity of these low‐valent metals, but examples of these MOFs remain exceedingly rare. The rational design of three‐dimensional MOFs with Pd0and Pt0nodes using tetratopic phosphine ligands is reported. Five new MOFs have been synthesized by systematic variation of the phosphine ligands and metal precursors employed, and these represent the first examples of MOFs constructed using phosphine–metal bonds as the sole structural component. The MOFs display solid‐state luminescence, with emission maxima that are significantly red‐shifted compared to Pd(PPh3)4. In addition, a RhIlow‐valent coordination solid based on the same linker design is reported, which displays solid‐state luminescence that is not observed for the molecular analogue.
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A Coordination Polymer of Vaska's Complex as a Heterogeneous Catalyst for the Reductive Formation of Enamines from Amides
Abstract Low‐valent metal–organic frameworks (LVMOFs) and related materials have gained interest due to their potential applications in heterogeneous catalysis. However, of the few LVMOFs that have been reported, none have shown catalytic activity. Herein, a low‐valent metal‐organic material constructed from phosphine linkers and IrInodes is reported. This material is effectively a crystalline, insoluble analogue of Vaska's complex. As such, the material reversibly binds O2and catalyzes the reductive formation of enamines from amides.
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- Award ID(s):
- 2153240
- PAR ID:
- 10415593
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 62
- Issue:
- 23
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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