Engineering topics
Deegan, Meaghan M.
Publications and source records attributed to Deegan, Meaghan M..
Manipulating solvent and solubility in the synthesis, activation, and modification of permanently porous coordination cages
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Synthesis, characterization, and polymerization of capped paddlewheel porous cages
Although paddlewheel-based structures are common among permanently porous metal–organic materials, suitable strategies for the isolation of metal node-terminated, capped paddlewheel-based cage structures remain limited. We explored the use of chelating dicarboxylate ligand derivates (esp) for the isolation of trimesate-linked cages, Mo 12 (btc) 4 (esp) 6 , that are structural analogs of the small octahedral pore of HKUST-1. The porosity of these novel cages is appreciably higher than that of previously reported structures of this type. We also demonstrate that pillaring the isolated cage with DABCO generated an amorphous polymer that featured exceptional thermal stability and enhanced porosity.
Dihydrogen Adduct (Co–H 2 ) Complexes Displaying H‐Atom and Hydride Transfer
Abstract The prototypical reactivity profiles of transition metal dihydrogen complexes (M‐H 2 ) are well‐characterized with respect to oxidative addition (to afford dihydrides, M(H) 2 ) and as acids, heterolytically delivering H + to a base and H − to the metal. In the course of this study we explored plausible alternative pathways for H 2 activation, namely direct activation through H‐atom or hydride transfer from the σ‐H 2 adducts. To this end, we describe herein the reactivity of an isostructural pair of a neutral S = and an anionic S =0 Co‐H 2 adduct, both supported by a trisphosphine borane ligand (P 3 B ). The thermally stable metalloradical, (P 3 B )Co(H 2 ), serves as a competent precursor for hydrogen atom transfer to t Bu 3 ArO ⋅ . What is more, its anionic derivative, the dihydrogen complex [(P 3 B )Co(H 2 )] 1− , is a competent precursor for hydride transfer to BEt 3 , establishing its remarkable hydricity. The latter finding is essentially without precedent among the vast number of M‐H 2 complexes known.
Dihydrogen Adduct (Co–H 2 ) Complexes Displaying H–Atom and Hydride Transfer
This work describes the synthesis of Isostructural Co(H 2 ) complexes that are unusual examples of neutral, S = 1/2 and anionic, S = 0 dihydrogen adducts. The reactivity of these species toward H-atom and hydride transfer is discussed in detail.
Using Low-Pressure Methane Adsorption Isotherms for Higher-Throughput Screening of Methane Storage Materials
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Structure and redox tuning of gas adsorption properties in calixarene-supported Fe( ii )-based porous cages
We describe the synthesis of Fe( ii )-based coordination cages whose stability and gas adsorption properties can be tuned through structural modifications and redox reactivity.