Dataset Information

An S = 1/2 Iron Complex Featuring N2, Thiolate, and Hydride Ligands: Reductive Elimination of H2 and Relevant Thermochemical Fe-H Parameters.

ABSTRACT: Believed to accumulate on the Fe sites of the FeMo-cofactor (FeMoco) of MoFe-nitrogenase under turnover, strongly donating hydrides have been proposed to facilitate N2 binding to Fe and may also participate in the hydrogen evolution process concomitant to nitrogen fixation. Here, we report the synthesis and characterization of a thiolate-coordinated FeIII(H)(N2) complex, which releases H2 upon warming to yield an FeII-N2-FeII complex. Bimolecular reductive elimination of H2 from metal hydrides is pertinent to the hydrogen evolution processes of both enzymes and electrocatalysts, but well-defined examples are uncommon and usually observed from diamagnetic second- and third-row transition metals. Kinetic data obtained on the HER of this ferric hydride species are consistent with a bimolecular reductive elimination pathway, arising from cleavage of the Fe-H bond with a computationally determined BDFE of 55.6 kcal/mol.

SUBMITTER: Gu NX

PROVIDER: S-EPMC6592702 | biostudies-literature | 2018 May

REPOSITORIES: biostudies-literature

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An S = 1/2 Iron Complex Featuring N2, Thiolate, and Hydride Ligands: Reductive Elimination of H2 and Relevant Thermochemical Fe-H Parameters.

Gu Nina X NX Oyala Paul H PH Peters Jonas C JC

Journal of the American Chemical Society 20180510 20

Believed to accumulate on the Fe sites of the FeMo-cofactor (FeMoco) of MoFe-nitrogenase under turnover, strongly donating hydrides have been proposed to facilitate N2 binding to Fe and may also participate in the hydrogen evolution process concomitant to nitrogen fixation. Here, we report the synthesis and characterization of a thiolate-coordinated FeIII(H)(N2) complex, which releases H2 upon warming to yield an FeII-N2-FeII ...[more]

PMID: 29684269

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Project description:Since their first description over a decade ago, organotin(ii) hydrides have been an iconic class of compounds in molecular main group chemistry. Among other approaches they have been accessed from the hydrogenation of distannynes. We herein report their accessibility from the other direction by dehydrogenation of organotin trihydride. On reacting pyridine and amine bases with the bulky substituted organotin trihydride Ar*SnH3 (Ar* = 2,6-trip2(C6H3)-, trip = 2,4,6-triisopropylphenyl) hydrogen evolution was observed. In case of catalytic amounts of base the dehydro-coupling product diorganodistannane Ar*H2SnSnH2Ar* was obtained quantitatively whilst for excessive amounts (>4 eq.) the monomeric base adduct to known Ar*SnH was obtained almost exclusively. The base adducts were found to be remarkably thermally robust. They readily react with polar fulvenic C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C-bonds in hydro-stannylenylation reactions. The resulting half-sandwich complex Ar*SnCp* was structurally characterized. Moreover, on application of less nucleophilic amine bases, the uncoordinated, in solution dimeric [Ar*SnH]2 is formed. NMR spectroscopic studies on the kinetics of the DMAP-catalysed reductive elimination of dihydrogen were performed. The activation energy was approximated to be 13.7 kcal mol-1. Solvent dependencies and a kinetic isotope effect KIE of kH/kD = 1.65 in benzene and 2.04 in THF were found and along with DFT calculations support a polar mechanism for this dehydrogenation.

Dataset Information

An S = 1/2 Iron Complex Featuring N2, Thiolate, and Hydride Ligands: Reductive Elimination of H2 and Relevant Thermochemical Fe-H Parameters.

Publications

An S = <sup>1</sup>/<sub>2</sub> Iron Complex Featuring N<sub>2</sub>, Thiolate, and Hydride Ligands: Reductive Elimination of H<sub>2</sub> and Relevant Thermochemical Fe-H Parameters.

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