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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. 

Controlled partial decomposition of 2-selenonicotinic acid in the presence of Co 2+ or Ni 2+ resulted in the in situ formation of an unusual MOF based on triselenane ligands (RSeSeSeR) coordinated to M 2+ centers as NSeN-pincers. Post-synthetic oxidation by treatment with aqueous H 2 O 2 facilitates its solid-state conversion into a RSeO 2 − molecular coordination complex, which was tracked via powder X-ray diffraction studies and by single-crystal structural resolution of the final product. 

β,β′-Phenylene bridged hexaphyrin[1.0.1.0.1.0] (naphthorosarin), an expanded porphyrin possessing C 3v -symmetry, has been shown to possess unique electronic features. We now report a bimetallic Rh( i )-complex of naphthorosarin retaining 24 π-antiaromatic characteristics. The two Rh( i ) cations reside on opposite sides of the macrocyclic π-system and are separated at a distance consistent with a possible Rh( i )–Rh( i ) metallic bond interaction. 

The synthesis and characterization of the alkylidenyl-dibenzihexaphyrins bearing four indanedionyl groups at the meso -positions linked via four meso -exocyclic double bonds is reported. Treatment with trifluoroacetic acid at 50 °C leads to C(α)-protonation of the two indanedionyl groups resulting increased macrocyclic conjugation with dramatic red shifted absorption spectra.