A Triad of Highly Reduced, Linear Iron Nitrosyl Complexes: {FeNO}^(8-10)

Given the importance of Fe–NO complexes in both human biology and the global nitrogen cycle, there has been interest in understanding their diverse electronic structures. Herein a redox series of isolable iron nitrosyl complexes stabilized by a tris(phosphine)borane (TPB) ligand is described. These structurally characterized iron nitrosyl complexes reside in the following highly reduced Enemark–Feltham numbers: {FeNO}^8, {FeNO}^9, and {FeNO}^(10). These {FeNO}^(8–10) compounds are each low-spin, and feature linear yet strongly activated nitric oxide ligands. Use of Mössbauer, EPR, NMR, UV/Vis, and IR spectroscopy, in conjunction with DFT calculations, provides insight into the electronic structures of this uncommon redox series of iron nitrosyl complexes. In particular, the data collectively suggest that {TPBFeNO}^(8–10) are all remarkably covalent. This covalency is likely responsible for the stability of this system across three highly reduced redox states that correlate with unusually high Enemark–Feltham numbers

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

Fe-Mediated Nitrogen Fixation with a Metallocene Mediator: Exploring pK_a Effects and Demonstrating Electrocatalysis

Substrate selectivity in reductive multi-electron/proton catalysis with small molecules such as N_2, CO_2, and O_2 is a major challenge for catalyst design, especially where the competing hydrogen evolution reaction (HER) is thermodynamically and kinetically competent. In this study, we investigate how the selectivity of a tris(phosphine)borane iron(I) catalyst, P_3^BFe^+, for catalyzing the nitrogen reduction reaction (N_2RR, N_2-to-NH_3 conversion) versus HER changes as a function of acid pK_a. We find that there is a strong correlation between pKa and N_2RR efficiency. Stoichiometric studies indicate that the anilinium triflate acids employed are only compatible with the formation of early stage intermediates of N_2 reduction (e.g., Fe(NNH) or Fe(NNH_2)) in the presence of the metallocene reductant Cp*_2Co. This suggests that the interaction of acid and reductant is playing a critical role in N–H bond forming reactions. DFT studies identify a protonated metallocene species as a strong PCET donor and suggest that it should be capable of forming the early stage N–H bonds critical for N_2RR. Furthermore, DFT studies also suggest that the observed pK_a effect on N_2RR efficiency is attributable to the rate and thermodynamics, of Cp*_2Co protonation by the different anilinium acids. Inclusion of Cp*_2Co^+ as a co-catalyst in controlled potential electrolysis experiments leads to improved yields of NH_3. The data presented provide what is to our knowledge the first unambiguous demonstration of electrocatalytic nitrogen fixation by a molecular catalyst (up to 6.7 equiv NH_3 per Fe at −2.1 V vs Fc^(+/0))

Catalytic N_2-to-NH_3 Conversion by Fe at Lower Driving Force: A Proposed Role for Metallocene-Mediated PCET

We have recently reported on several Fe catalysts for N_2-to-NH_3 conversion that operate at low temperature (−78 °C) and atmospheric pressure while relying on a very strong reductant (KC_8) and acid ([H(OEt_2)_2][BArF_4]). Here we show that our original catalyst system, P_3^BFe, achieves both significantly improved efficiency for NH_3 formation (up to 72% for e^– delivery) and a comparatively high turnover number for a synthetic molecular Fe catalyst (84 equiv of NH_3 per Fe site), when employing a significantly weaker combination of reductant (Cp*_2Co) and acid ([Ph_2NH_2][OTf] or [PhNH_3][OTf]). Relative to the previously reported catalysis, freeze-quench Mössbauer spectroscopy under turnover conditions suggests a change in the rate of key elementary steps; formation of a previously characterized off-path borohydrido–hydrido resting state is also suppressed. Theoretical and experimental studies are presented that highlight the possibility of protonated metallocenes as discrete PCET reagents under the present (and related) catalytic conditions, offering a plausible rationale for the increased efficiency at reduced driving force of this Fe catalyst system

Examination of Acid-Fast Bacilli in Sputum Using Modified Light Microscope with Homemade Light Emitting Diode Additional Attachment

Typical clinical symptoms and chest X-ray is a marker of Tuberculosis (TB) sufferers. However, the diagnosis of TB in adults should be supported by microscopic examination. Currently, Bacilli microscopic examination of acid-fast bacilli (AFB) in sputum by Ziehl-Neelsen (ZN) coloring is the most widely used. However, for reasons of convenience, especially for laboratories with a considerable amount of smear samples, and due to higher sensitivity compared with ZN staining, the World Health Organization (WHO) has recommended the use of auramine-O-staining (fluorochrome &nbsp;staining), which is visualized by light emitting diode (LED) fluorescence microscopy. The aim of this study was to evaluate the performance of modified light microscope with homemade LED additional attachment for examination of AFB in sputum using auramine-O-staining method. We compared the sensitivity and specificity of 2 kinds of AFB in sputum methods: ZN and fluorochrome, using culture on Lowenstein-Jensen media as the gold standard. The results showed auramine-O-staining gives more proportion of positive findings (81%) compared to the ZN method (70%). These results demonstrated that the sensitivity of auramine-O-staining was higher than ZN, however it gives more potential false positive results than ZN. The sensitivity of auramine-O-staining in detecting AFB in sputum was 100% while the specificity was 88%

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

Fe-Mediated Nitrogen Fixation with a Metallocene Mediator: Exploring pK_a Effects and Demonstrating Electrocatalysis

Substrate selectivity in reductive multi-electron/proton catalysis with small molecules such as N_2, CO_2, and O_2 is a major challenge for catalyst design, especially where the competing hydrogen evolution reaction (HER) is thermodynamically and kinetically competent. In this study, we investigate how the selectivity of a tris(phosphine)borane iron(I) catalyst, P_3^BFe^+, for catalyzing the nitrogen reduction reaction (N_2RR, N_2-to-NH_3 conversion) versus HER changes as a function of acid pK_a. We find that there is a strong correlation between pKa and N_2RR efficiency. Stoichiometric studies indicate that the anilinium triflate acids employed are only compatible with the formation of early stage intermediates of N_2 reduction (e.g., Fe(NNH) or Fe(NNH_2)) in the presence of the metallocene reductant Cp*_2Co. This suggests that the interaction of acid and reductant is playing a critical role in N–H bond forming reactions. DFT studies identify a protonated metallocene species as a strong PCET donor and suggest that it should be capable of forming the early stage N–H bonds critical for N_2RR. Furthermore, DFT studies also suggest that the observed pK_a effect on N_2RR efficiency is attributable to the rate and thermodynamics, of Cp*_2Co protonation by the different anilinium acids. Inclusion of Cp*_2Co^+ as a co-catalyst in controlled potential electrolysis experiments leads to improved yields of NH_3. The data presented provide what is to our knowledge the first unambiguous demonstration of electrocatalytic nitrogen fixation by a molecular catalyst (up to 6.7 equiv NH_3 per Fe at −2.1 V vs Fc^(+/0))

Exploring the Limits of Dative Boratrane Bonding: Iron as a Strong Lewis Base in Low-Valent Non-Heme Iron-Nitrosyl Complexes

We previously reported the synthesis and preliminary characterization of a unique series of low-spin (ls) {FeNO}⁸⁻¹⁰ complexes supported by an ambiphilic trisphosphineborane ligand, [Fe(TPB)(NO)]^(+/0/−). Herein, we use advanced spectroscopic techniques and density functional theory (DFT) calculations to extract detailed information as to how the bonding changes across the redox series. We find that, in spite of the highly reduced nature of these complexes, they feature an NO+ ligand throughout with strong Fe−NO π-backbonding and essentially closed-shell electronic structures of their FeNO units. This is enabled by an Fe−B interaction that is present throughout the series. In particular, the most reduced [Fe(TPB)(NO)]− complex, an example of a ls-{FeNO}¹⁰ species, features a true reverse dative Fe → B bond where the Fe center acts as a strong Lewis-base. Hence, this complex is in fact electronically similar to the ls-{FeNO}⁸ system, with two additional electrons “stored” on site in an Fe−B single bond. The outlier in this series is the ls-{FeNO}⁹ complex, due to spin polarization (quantified by pulse EPR spectroscopy), which weakens the Fe−NO bond. These data are further contextualized by comparison with a related N₂ complex, [Fe(TPB)(N₂)]⁻, which is a key intermediate in Fe(TPB)-catalyzed N₂ fixation. Our present study finds that the Fe → B interaction is key for storing the electrons needed to achieve a highly reduced state in these systems, and highlights the pitfalls associated with using geometric parameters to try to evaluate reverse dative interactions, a finding with broader implications to the study of transition metal complexes with boratrane and related ligands

Exploring the Limits of Dative Boratrane Bonding: Iron as a Strong Lewis Base in Low-Valent Non-Heme Iron-Nitrosyl Complexes

We previously reported the synthesis and preliminary characterization of a unique series of low-spin (ls) {FeNO}⁸⁻¹⁰ complexes supported by an ambiphilic trisphosphineborane ligand, [Fe(TPB)(NO)]^(+/0/−). Herein, we use advanced spectroscopic techniques and density functional theory (DFT) calculations to extract detailed information as to how the bonding changes across the redox series. We find that, in spite of the highly reduced nature of these complexes, they feature an NO+ ligand throughout with strong Fe−NO π-backbonding and essentially closed-shell electronic structures of their FeNO units. This is enabled by an Fe−B interaction that is present throughout the series. In particular, the most reduced [Fe(TPB)(NO)]− complex, an example of a ls-{FeNO}¹⁰ species, features a true reverse dative Fe → B bond where the Fe center acts as a strong Lewis-base. Hence, this complex is in fact electronically similar to the ls-{FeNO}⁸ system, with two additional electrons “stored” on site in an Fe−B single bond. The outlier in this series is the ls-{FeNO}⁹ complex, due to spin polarization (quantified by pulse EPR spectroscopy), which weakens the Fe−NO bond. These data are further contextualized by comparison with a related N₂ complex, [Fe(TPB)(N₂)]⁻, which is a key intermediate in Fe(TPB)-catalyzed N₂ fixation. Our present study finds that the Fe → B interaction is key for storing the electrons needed to achieve a highly reduced state in these systems, and highlights the pitfalls associated with using geometric parameters to try to evaluate reverse dative interactions, a finding with broader implications to the study of transition metal complexes with boratrane and related ligands