Characterization of the earliest intermediate of Fe-N_2 protonation: CW and Pulse EPR detection of an Fe-NNH species and its evolution to Fe-NNH_2^+

Iron diazenido species (Fe(NNH)) have been proposed as the earliest intermediates of catalytic N_2-to-NH_3 conversion (N_2RR) mediated by synthetic iron complexes and relatedly as intermediates of N_2RR by nitrogenase enzymes. However, direct identification of such iron species, either during or independent of catalysis, has proven challenging owing to their high degree of instability. The isolation of more stable silylated diazenido analogues, Fe(NNSiR_3), and also of further downstream intermediates (e.g., Fe(NNH_2)), nonetheless points to Fe(NNH) as the key first intermediate of protonation in synthetic systems. Herein we show that low-temperature protonation of a terminally bound Fe-N_2– species, supported by a bulky trisphosphinoborane ligand (^(Ar)P_3^B), generates an S = 1/2 terminal Fe(NNH) species that can be detected and characterized by continuous-wave (CW) and pulse EPR techniques. The ^1H-hyperfine for ^(Ar)P_3^BFe(NNH) derived from the presented ENDOR studies is diagnostic for the distally bound H atom (a_(iso) = 16.5 MHz). The Fe(NNH) species evolves further to cationic [Fe(NNH_2)]+ in the presence of additional acid, the latter being related to a previously characterized [Fe(NNH_2)]+ intermediate of N2RR mediated by a far less encumbered iron tris(phosphine)borane catalyst. While catalysis is suppressed in the present sterically very crowded system, N_2-to-NH_3 conversion can nevertheless be demonstrated. These observations in sum add support to the idea that Fe(NNH) plays a central role as the earliest intermediate of Fe-mediated N2RR in a synthetic system

Terminal Molybdenum Phosphides with d Electrons: Radical Character Promotes Coupling Chemistry

A terminal Mo phosphide was prepared via group transfer of both P- and Cl-atoms from chloro-substituted dibenzo-7λ^3-phosphanorbornadiene. This compound represents the first structurally characterized terminal transition metal phosphide with valence d electrons. In the tetragonal ligand field, these electrons populate an orbital of d_(xy) parentage, an electronic configuration that accommodates both metal d-electrons and a formal M≡P triple bond. Single electron oxidation affords a transient open shell terminal phosphide cation with significant spin density on P, as corroborated by CW and pulsed EPR characterization. Facile P-P bond formation occurs from this species via intermolecular phosphide coupling

An S = ½ iron complex featuring N₂, thiolate, and hydride ligands: Reductive elimination of H₂ and relevant thermochemical Fe-H parameters

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 Fe^(III)(H)(N₂) complex, which releases H₂ upon warming to yield an Fe^(II)–N₂–Fe^(II) 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

Hydrazine Formation via Coupling of a Ni^(III)-NH₂ Radical

M(NH_x) intermediates involved in N–N bond formation are central to ammonia oxidation (AO) catalysis, an enabling technology to ultimately exploit ammonia (NH₃) as an alternative fuel source. While homocoupling of a terminal amide species (M–NH₂) to form hydrazine (N₂H₄) has been proposed, well‐defined examples are without precedent. Herein, we discuss the generation and electronic structure of a Ni^(III)–NH₂ species that undergoes bimolecular coupling to generate a Ni^(II)₂(N₂H₄) complex. This hydrazine adduct can be further oxidized to a structurally unusual Ni₂(N₂H₂) species; the latter releases N₂ in the presence of NH₃, thus establishing a synthetic cycle for Ni‐mediated AO. Distribution of the redox load for H₂N–NH₂ formation via NH₂ coupling between two metal centers presents an attractive strategy for AO catalysis using Earth‐abundant, late first‐row metals

H₂ Evolution from a Thiolate-Bound Ni(III) Hydride

Terminal Ni^(III) hydrides are proposed intermediates in proton reduction catalyzed by both molecular electrocatalysts and metalloenzymes, but well-defined examples of paramagnetic nickel hydride complexes are largely limited to bridging hydrides. Herein, we report the synthesis of an S = 1/2, terminally bound thiolate–Ni^(III)–H complex. This species and its terminal hydride ligand in particular have been thoroughly characterized by vibrational and EPR techniques, including pulse EPR studies. Corresponding DFT calculations suggest appreciable spin leakage onto the thiolate ligand. The hyperfine coupling to the terminal hydride ligand of the thiolate–Ni^(III)–H species is comparable to that of the hydride ligand proposed for the Ni–C hydrogenase intermediate (Ni^(III)–H–Fe^(II)). Upon warming, the featured thiolate–Ni^(III)–H species undergoes bimolecular reductive elimination of H₂. Associated kinetic studies are discussed and compared with a structurally related Fe^(III)–H species that has also recently been reported to undergo bimolecular H–H coupling

Cp* Noninnocence Leads to a Remarkably Weak C–H Bond via Metallocene Protonation

Metallocenes, including their permethylated variants, are extremely important in organometallic chemistry. In particular, many are synthetically useful either as oxidants (e.g., Cp_2Fe^+) or as reductants (e.g., Cp_2Co, Cp*_2Co, and Cp*_2Cr). The latter have proven to be useful reagents in the reductive protonation of small-molecule substrates, including N_2. As such, understanding the behavior of these metallocenes in the presence of acids is paramount. In the present study, we undertake the rigorous characterization of the protonation products of Cp*_2Co using pulse electron paramagnetic resonance (EPR) techniques at low temperature. We provide unequivocal evidence for the formation of the ring-protonated isomers Cp*(exo/endo-η^4-C_5Me_5H)Co^+. Variable temperature Q-band (34 GHz) pulse EPR spectroscopy, in conjunction with density functional theory (DFT) predictions, are key to reliably assigning the Cp*(exo/endo-η^4-C_5Me_5H)Co^+ species. We also demonstrate that exo-protonation selectivity can be favored by using a bulkier acid and suggest this species is thus likely a relevant intermediate during catalytic nitrogen fixation given the bulky anilinium acids employed. Of further interest, we provide physical data to experimentally assess the C–H bond dissociation free energy (BDFE_(C–H)) for Cp*(exo-η^4-C_5Me_5H)Co^+. These experimental data support our prior DFT predictions of an exceptionally weak C–H bond (<29 kcal mol^(–1)), making this system among the most reactive (with respect to C–H bond strength) to be thoroughly characterized. These data also point to the propensity of Cp*(exo-η^4-C_5Me_5H)Co to mediate hydride (H–) transfer. Our findings are not limited to the present protonated metallocene system. Accordingly, we outline an approach to rationalizing the reactivity of arene-protonated metal species, using decamethylnickelocene as an additional example

S = 3 Ground State for a Tetranuclear Mn^(IV)₄O₄ Complex Mimicking the S₃ State of the Oxygen Evolving Complex

The S₃ state is currently the last observable intermediate prior to O–O bond formation at the oxygen-evolving complex (OEC) of Photosystem II, and its electronic structure has been assigned to a homovalent Mn^(IV)₄ core with an S = 3 ground state. While structural interpretations based on the EPR spectroscopic features of the S₃ state provide valuable mechanistic insight, corresponding synthetic and spectroscopic studies on tetranuclear complexes mirroring the Mn oxidation states of the S₃ state remain rare. Herein, we report the synthesis and characterization by XAS and multifrequency EPR spectroscopy of a Mn^(IV)₄O₄ cuboidal complex as a spectroscopic model of the S₃ state. Results show that this Mn^(IV)₄O₄ complex has an S = 3 ground state with isotropic ⁵⁵Mn hyperfine coupling constants of −75, −88, −91, and 66 MHz. These parameters are consistent with an αααβ spin topology approaching the trimer–monomer magnetic coupling model of pseudo-octahedral Mn^(IV) centers. Importantly, the spin ground state changes from S = 1/2 to S = 3 as the OEC is oxidized from the S₂ state to the S₃ state. This same spin state change is observed following oxidation of the previously reported Mn^(III)Mn^(IV)₃O₄ cuboidal complex to the Mn^(IV)₄O₄ complex described here. This sets a synthetic precedent for the observed low-spin to high-spin conversion in the OEC

Snapshots of a Migrating H-Atom: Characterization of a Reactive Iron(III) Indenide Hydride and its Nearly Isoenergetic Ring-Protonated Iron(I) Isomer

We report the characterization of an S=1/2 iron π‐complex, [Fe(η⁶‐IndH)(depe)]⁺ (Ind=Indenide (C₉H₇⁻), depe=1,2‐bis(diethylphosphino)ethane), which results via C−H elimination from a transient Fe^(III) hydride, [Fe(η³:η²‐Ind)(depe)H]⁺. Owing to weak M−H/C−H bonds, these species appear to undergo proton‐coupled electron transfer (PCET) to release H₂ through bimolecular recombination. Mechanistic information, gained from stoichiometric as well as computational studies, reveal the open‐shell π‐arene complex to have a BDFE_(C‐H) value of ≈50 kcal mol⁻¹, roughly equal to the BDFE_(Fe‐H) of its Fe^(III)−H precursor (ΔG°≈0 between them). Markedly, this reactivity differs from related Fe(η⁵‐Cp/Cp*) compounds, for which terminal Fe^(III)−H cations are isolable and have been structurally characterized, highlighting the effect of a benzannulated ring (indene). Overall, this study provides a structural, thermochemical, and mechanistic foundation for the characterization of indenide/indene PCET precursors and outlines a valuable approach for the differentiation of a ring‐ versus a metal‐bound H‐atom by way of continuous‐wave (CW) and pulse EPR (HYSCORE) spectroscopic measurements

Cp* Noninnocence Leads to a Remarkably Weak C–H Bond via Metallocene Protonation

Metallocenes, including their permethylated variants, are extremely important in organometallic chemistry. In particular, many are synthetically useful either as oxidants (e.g., Cp_2Fe^+) or as reductants (e.g., Cp_2Co, Cp*_2Co, and Cp*_2Cr). The latter have proven to be useful reagents in the reductive protonation of small-molecule substrates, including N_2. As such, understanding the behavior of these metallocenes in the presence of acids is paramount. In the present study, we undertake the rigorous characterization of the protonation products of Cp*_2Co using pulse electron paramagnetic resonance (EPR) techniques at low temperature. We provide unequivocal evidence for the formation of the ring-protonated isomers Cp*(exo/endo-η^4-C_5Me_5H)Co^+. Variable temperature Q-band (34 GHz) pulse EPR spectroscopy, in conjunction with density functional theory (DFT) predictions, are key to reliably assigning the Cp*(exo/endo-η^4-C_5Me_5H)Co^+ species. We also demonstrate that exo-protonation selectivity can be favored by using a bulkier acid and suggest this species is thus likely a relevant intermediate during catalytic nitrogen fixation given the bulky anilinium acids employed. Of further interest, we provide physical data to experimentally assess the C–H bond dissociation free energy (BDFE_(C–H)) for Cp*(exo-η^4-C_5Me_5H)Co^+. These experimental data support our prior DFT predictions of an exceptionally weak C–H bond (<29 kcal mol^(–1)), making this system among the most reactive (with respect to C–H bond strength) to be thoroughly characterized. These data also point to the propensity of Cp*(exo-η^4-C_5Me_5H)Co to mediate hydride (H–) transfer. Our findings are not limited to the present protonated metallocene system. Accordingly, we outline an approach to rationalizing the reactivity of arene-protonated metal species, using decamethylnickelocene as an additional example

Generating Potent C–H PCET Donors: Ligand-Induced Fe-to-Ring Proton Migration from a Cp*Fe^(III)–H Complex Demonstrates a Promising Strategy

Highly reactive organometallic species that mediate reductive proton-coupled electron transfer (PCET) reactions are an exciting area for development in catalysis, where a key objective focuses on tuning the reactivity of such species. This work pursues ligand-induced activation of a stable organometallic complex toward PCET reactivity. This is studied via the conversion of a prototypical Cp*Fe^(III)–H species, [Fe^(III)(η⁵-Cp*)(dppe)H]⁺ (Cp* = C₅Me₅⁻, dppe = 1,2-bis(diphenylphosphino)ethane), to a highly reactive, S = 1/2 ring-protonated endo-Cp*H–Fe relative, triggered by the addition of CO. Our assignment of the latter ring-protonated species contrasts with its previous reported formulation, which instead assigned it as a hypervalent 19-electron hydride, [Fe^(III)(η⁵-Cp*)(dppe)(CO)H]⁺. Herein, pulse EPR spectroscopy (^(1,2)H HYSCORE, ENDOR) and X-ray crystallography, with corresponding DFT studies, cement its assignment as the ring-protonated isomer, [Fe^I(endo-η⁴-Cp*H)(dppe)(CO)] ⁺. A less sterically shielded and hence more reactive exo-isomer can be generated through oxidation of a stable Fe0(exo-η⁴-Cp*H)(dppe)(CO) precursor. Both endo- and exo-ring-protonated isomers are calculated to have an exceptionally low bond dissociation free energy (BDFE_(C–H) ≈ 29 kcal mol⁻¹ and 25 kcal mol⁻¹, respectively) cf. BDFE_(Fe–H) of 56 kcal mol⁻¹ for [Fe^(III)(η⁵-Cp*)(dppe)H] ⁺. These weak C–H bonds are shown to undergo proton-coupled electron transfer (PCET) to azobenzene to generate diphenylhydrazine and the corresponding closed-shell [Fe^(II)(η⁵-Cp*)(dppe)CO]⁺ byproduct