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  1. Free, publicly-accessible full text available August 28, 2025
  2. The reactivity of the novel Re( i ) catalyst [Re( C12 Anth-py 2 )(CO) 3 Br] is modulated by its interactions with the covalent organic framework (COF) TFB-BD. The complex catalyzes either reductive etherification, oxidative esterification, or transfer hydrogenation depending on its local environment (embedded in TFB-BD, in homogeneous solution or co-incubated with TFB-BD, respectively). The results highlight that COFs can drastically modulate the reactivity of homogeneous catalysts. 
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  3. We report the synthesis and reactivity of a model of [Fe]-hydrogenase derived from an anthracene-based scaffold that includes the endogenous, organometallic acyl(methylene) donor. In comparison to other non-scaffolded acyl-containing complexes, the complex described herein retains molecularly well-defined chemistry upon addition of multiple equivalents of exogenous base. Clean deprotonation of the acyl(methylene) C–H bond with a phenolate base results in the formation of a dimeric motif that contains a new Fe–C(methine) bond resulting from coordination of the deprotonated methylene unit to an adjacent iron center. This effective second carbanion in the ligand framework was demonstrated to drive heterolytic H 2 activation across the Fe( ii ) center. However, this process results in reductive elimination and liberation of the ligand to extrude a lower-valent Fe–carbonyl complex. Through a series of isotopic labelling experiments, structural characterization (XRD, XAS), and spectroscopic characterization (IR, NMR, EXAFS), a mechanistic pathway is presented for H 2 /hydride-induced loss of the organometallic acyl unit ( i.e. pyCH 2 –CO → pyCH 3 +CO). The known reduced hydride species [HFe(CO) 4 ] − and [HFe 3 (CO) 11 ] − have been observed as products by 1 H/ 2 H NMR and IR spectroscopies, as well as independent syntheses of PNP[HFe(CO) 4 ]. The former species ( i.e. [HFe(CO) 4 ] − ) is deduced to be the actual hydride transfer agent in the hydride transfer reaction (nominally catalyzed by the title compound) to a biomimetic substrate ([ Tol Im](BAr F ) = fluorinated imidazolium as hydride acceptor). This work provides mechanistic insight into the reasons for lack of functional biomimetic behavior (hydride transfer) in acyl(methylene)pyridine based mimics of [Fe]-hydrogenase. 
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