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Abstract With the goal of generating anionic analogues to MN2S2⋅Mn(CO)3Br we introduced metallodithiolate ligands, MN2S22−prepared from the Cys‐X‐Cys biomimetic, ema4−ligand (ema=N,N′‐ethylenebis(mercaptoacetamide); M=NiII, [VIV≡O]2+and FeIII) to Mn(CO)5Br. An unexpected, remarkably stable dimanganese product, (H2N2(CH2C=O(μ‐S))2)[Mn(CO)3]2resulted from loss of M originally residing in the N2S24−pocket, replaced by protonation at the amido nitrogens, generating H2ema2−. Accordingly, the ema ligand has switched its coordination mode from an N2S24−cavity holding a single metal, to a binucleating H2ema2−with bridging sulfurs and carboxamide oxygens within Mn‐μ‐S‐CH2‐C‐O, 5‐membered rings. In situ metal‐templating by zinc ions gives quantitative yields of the Mn2product. By computational studies we compared the conformations of “linear” ema4−to ema4−frozen in the “tight‐loop” around single metals, and to the “looser” fold possible for H2ema2−that is the optimal arrangement for binucleation. XRD molecular structures show extensive H‐bonding at the amido‐nitrogen protons in the solid state.
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Synthesis and characterization of a ruthenium-containing copolymer for use as a photoredox catalyst
We present a [Ru(bpy)2(dmbpy)]2+- and pyrene-based photocatalytic PMMA that enables photoredox-energy transfer to achieve the C–H arylation of electron deficient aryl bromides.
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- Award ID(s):
- 2046470
- PAR ID:
- 10483402
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Polymer Chemistry
- Volume:
- 14
- Issue:
- 39
- ISSN:
- 1759-9954
- Page Range / eLocation ID:
- 4560 to 4568
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D3PY00428G
