NH Bond Research Articles

A theoretical investigation of the catalytic decomposition of hydroxylamine nitrate on Ir(1 1 0) surface

Hydroxylamine nitrate (HAN) based propellant, with high energy performance and non-toxic, is regarded as an ideal propellant for monopropellant rocket engine. Density functional theory calculation was carried out to investigate the catalytic decomposition of HAN on Ir(110) surface. The optimized adsorption configurations and decomposition pathways of HAN on Ir(110) were calculated. Four different adsorption configurations and their decomposition pathways over Ir(110) have been found. The transformation of H from HNO3 to NH2OH happens in all adsorption configurations. In most situations, the decomposition of HAN starts with the scission of NO bond in NH3OH+ group. NH, OH, H2O and NO2 are the decomposition product. Compared with the barrier energy of each elementary reaction, the scission of NO bond in NO3– group is key to the decomposition rate of HAN. Among all products, NO2 and NH can be decomposed into N, O and H by scission of NO bond and NH bond.

Low loss SiN films for integrated photonics deposited by PVD at low temperature

Integration of SiN films with Si photonics platforms is attractive for the 3D integration of multiple waveguide levels in optical routing circuits. This paper reports on the optical characterization of SiN films deposited by PVD and PECVD with the STMicroelectronics 300 mm Photonic R&D platform at CMOS-compatible temperatures. SiN deposition was engineered to reduce the propagation losses caused by 2nd harmonic vibrational absorption of NH bonds.

Hydrogen production from ammonia decomposition catalyzed by Ru nano-particles in alkaline molecular sieves under photothermal conditions

Because the high electron cloud density around Ru is favorable for ammonia decomposition, gallium addition to it resulted in an alkaline molecular sieve carrier with a large specific surface area. It was revealed that GaOH not only elevated the electron cloud density near the active center of Ru but also encouraged NH bond breaking and hydrogen atoms’ binding on the catalyst surface. Furthermore, the molecular sieve's regular pore structure strongly inhibited the growth of Ru particles within it, resulting in a high degree of mono-dispersion of Ru nanoparticles and a reduction in the average particle size of the Ru active center to < 3 nm. For TOF >1, the above two factors combined to decrease the ammonia decomposition temperature to < 450 °C. Furthermore, under photothermal synergistic catalysis, the hydrogen production rate via ammonia decomposition was further elevated, and the reaction temperature was further decreased to < 380 °C with TOF > 1. In situ UV photoelectron spectroscopy clarified that the hydrogen atom concentration on Ru increased during photothermal catalysis. According to the FT-IR analysis of the surface intermediate of NH/NH2 formed by ammonia decomposition, photothermal synergistic catalysis can weaken the NH bond compared with pure heating, making it easier for H atoms to combine and form H2. The test results of the correlation between activation energy, reaction rate, and ammonia partial pressure show that, when compared to pure thermal catalysis, photothermal catalysis does not substantially alter the reaction path. The primary reason behind the increased hydrogen production rate of ammonia decomposition by photothermal catalysis was the thermal effect of the light source.

Accelerated isothermal decomposition behavior derived from the interaction of 3,4-dinitrofurazanfuroxan (DNTF) with amino nitrogen-rich compounds

The mechanism underlying the isothermal decomposition of DNTF in various amino nitrogen-rich compounds was explored in this work. Results showed interactions between DNTF and the hybrid systems of nitrogen-rich molecules containing NH bonds, and these interactions accelerated the decomposition of DNTF. The kinetic parameters of the samples at the pre-decomposition stage were calculated under isothermal conditions, and the results confirmed that the activation energy of the hybrid system was significantly lower than that of the DNTF monosystem. According to FT-IR and HPLC measurements, it was found that the decomposition rate of DNTF in hybrid system was faster than that of AMTZ, and that the furoxan ring broke first, followed by the accelerated decomposition of AMTZ, which also indicated that AMTZ could accelerate the decomposition of DNTF, and they may have promoted each other's decomposition.

Metal-organic framework modified PEO-based solid electrolyte for high-performance all-solid-state lithium metal batteries

All-solid-state lithium metal batteries (ASSLMBs) are expected to provide a next-generation solution for energy storage. However, intrinsic low ionic conductivity of PEO-based electrolyte causes inferior capacity seriously hinders their widespread commercial application. Here, a new kind of solid electrolyte is explored by incorporation of PEO with metal–organic framework ZIF-67 to enhance the ionic conductivity to 1 × 10-4 S cm−1 at room temperature. Lewis acid-base interaction that forms between Co element and TFSI- promotes the dissociation of lithium salt and enhances Li+ transport. Moreover, NH bonds of ZIF-67 combine with the lone pair of electrons of O on the PEO segment to form hydrogen bonds (NH…O), reducing the strong interaction between Li+ and PEO. The cathode with 6 mg cm−2 of LiFePO4 loading delivers a high capacity of 129.7 mAhg-1 at 0.1C. Furthermore, the assembled batteries delivered a capacity of 147 mAhg-1 at room temperature after 300 cycles.

Hydrogen bonds of OCNH motif in rings in drugs: A molecular electrostatic potential analysis.

The OCNH unit is one of the most frequently encountered structural motifs in rings in drugs which serves dual role as the proton donor through NH bond and proton acceptor through the CO bond. Here, we predicted the HB strength (Eint ) of OCNH motif with H2 O for commonly observed 37 rings in drugs with DFT method M06L/6-311++G(d,p). The HB strength is rationalized in terms of molecular electrostatic potential (MESP) topology parameters ΔVn(NH) and ΔVn(CO) which describe the relative electron deficient/rich nature of NH and CO, respectively, with respect to the reference formamide. The Eint of formamide is -10.0 kcal/mol whereas the Eint of ring systems is in the range -8.6 to -12.7 kcal/mol-a minor increase/decrease compared to the formamide. The variations in Eint are addressed using the MESP parameters ΔVn(NH) and ΔVn(CO) and proposed the hypothesis that a positive ΔVn(NH) enhances NH…Ow interaction while a negative ΔVn(CO) enhances the CO…Hw interaction. The hypothesis is proved by expressing Eint jointly as ΔVn(NH) and ΔVn(CO) and also verified for twenty FDA approved drugs. The predicted Eint for the drugs using ΔVn(NH) and ΔVn(CO) agreed well with the calculated Eint . The study confirms that even delicate variations in the electronic feature of a molecule can be quantified in terms of MESP parameters and they provide a priori prediction of the HB strength. The MESP topology analysis is recommended to understand the tunability of HB strength in drug motifs.

Isolated Cu-N5 sites engineered polypyrrole-reduced graphene oxide hybrids for enhancing room-temperature DMMP sensing

The hydrogen bonding interactions are potentially employed to fabricate high-performance room-temperature gas sensors for detection of organophosphorus. Nevertheless, the low response toward target gases of conventional sensing materials hinders their further applications. Herein, an isolated Cu-N5 sites engineering strategy is reported to improve sensing performances for polypyrrole-reduced graphene oxide hybrids (PPy-rGO)-based room-temperature dimethyl methyl phosphate (DMMP) sensors. The isolated Cu-N5 sites were simply constructed by adsorption of Cu2+ ions with PPy-rGO hybrids owing to strong metal-support interactions. X-ray absorption fine structure analysis indicates that Cux+ ions with mean chemical valence of + 1.07 nearly atomically distributed on support with coordination structure of Cu-N5. Benefiting from the structure regulation by Cux+ ions, as-constructed DMMP sensor demonstrated 4.5-fold improvement in response to 100 ppm DMMP and 2.5-fold improvement in limit of detection, compared to PPy-rGO hybrids. The density functional theory, spectroscopic characterizations and quartz crystal microbalance tests prove that the construction of Cu-N5 sites not only heightens hydrogen bonding interactions between NH bonds and DMMP molecules induced by newly formed coordination interactions between Cux+ ions and NH bonds, but also serves as new active sites for adsorption of DMMP molecules. This work offers a new avenue for developing high-performance room-temperature gas sensors by heightening hydrogen bonding interactions.

Dual Photochemistry of Benzimidazole.

Monomers of benzimidazole trapped in an argon matrix at 15 K were characterized by vibrational spectroscopy and identified as 1H-tautomers exclusively. The photochemistry of matrix-isolated 1H-benzimidazole was induced by excitations with a frequency-tunable narrowband UV light and followed spectroscopically. Hitherto unobserved photoproducts were identified as 4H- and 6H-tautomers. Simultaneously, a family of photoproducts bearing the isocyano moiety was identified. Thereby, the photochemistry of benzimidazole was hypothesized to follow two reaction pathways: the fixed-ring and the ring-opening isomerizations. The former reaction channel results in the cleavage of the NH bond and formation of a benzimidazolyl radical and an H-atom. The latter reaction channel involves the cleavage of the five-membered ring and concomitant shift of the H-atom from the CH bond of the imidazole moiety to the neighboring NH group, leading to 2-isocyanoaniline and subsequently to the isocyanoanilinyl radical. The mechanistic analysis of the observed photochemistry suggests that detached H-atoms, in both cases, recombine with the benzimidazolyl or isocyanoanilinyl radicals, predominantly at the positions with the largest spin density (revealed using the natural bond analysis computations). The photochemistry of benzimidazole therefore occupies an intermediate position between the earlier studied prototype cases of indole and benzoxazole, which exhibit exclusively the fixed-ring and the ring-opening photochemistries, respectively.

Simultaneous defect passivation and energy level modulation by multifunctional phthalocyanine for efficient and stable perovskite solar cells

Interface passivation is an effective means to decrease detrimental defects and realize highly efficient and stable perovskite solar cells (PSCs). Nevertheless, most of the interfacial passivators currently used are easily formed mismatched energy levels and impede the extraction of photogenerated charge carriers. Herein, a metal-free H2-phthalocyanine (H2Pc) is reported to passivate the interface defects and improve the crystallinity and energy level alignment. Contrasting metal Zn-phthalocyanine, the pyrrolic nitrogen and NH bond in the structure of the H2Pc molecule exhibit a higher capability to interact with unsaturated Pb and I site. It is found that the defects passivation and improved crystallinity in H2Pc molecule treatment are achieved by the formation of coordination bonding between N atoms and uncoordinated Pb2+ ions and hydrogen bonding between NH bond and I (iodine). Simultaneously, the H2Pc treatment can also improve energy level alignment and promote the charge extraction from perovskite to the hole transport material layer. As a result, a champion power conversion efficiency (PCE) of 20.59 % is achieved for the H2Pc PSCs, which is higher than that of 18.54 % for the ZnPc PSCs and 16.50 % for the pristine PSCs. Meanwhile, the H2Pc device shows significantly improved moisture, thermal, and illumination stability and with retaining over 90 % of its initial PCE after aging for 1000 h at about 20 % relative humidity in ambient conditions. The present work provides a practical and efficient method of simultaneous defect passivation and energy level modulation and toward the purpose of attaining superior performance PSCs and other perovskite-based electronics.

Direct Activation of the C(sp3)-NH2 Bond of Primary Aliphatic Alkylamines by a High-Valent CoIII,IV2(μ-O)2 Diamond Core Complex.

Aliphatic alkylamines are abundant feedstock and versatile building blocks for many organic transformations. While remarkable progress has been made to construct C-N bonds on aliphatic and aromatic carbon centers, the activation and functionalization of C(sp3)-NH2 bonds in primary alkylamines remain a challenging process. In the present work, we discovered an unprecedented method to directly activate the C(sp3)-NH2 bond of primary alkylamines by a high-valent dinuclear CoIII,IV2(μ-O)2 diamond core complex. This reaction results in the installation of other functional groups such as halides and alkenes onto the α-carbon center concomitant with the 2-e- oxidation of the nitrogen atom on the amino group to form NH2OH. These results shed light on future development enabling versatile functionalization of primary alkylamines based on the dinuclear cobalt system. Moreover, our work suggests that a related high-valent copper-oxo intermediate is likely generated in the ammonia monooxygenase catalytic cycle to affect the oxidation of NH3 to NH2OH.

Anodized screen-printed electrode modified with poly(5-amino-4H-1,2,4-triazole-3-thiol) film for ultrasensitive detection of Hg2+ in fish samples

Anodized screen-printed electrode (ASPE) was modified by electrochemical polymerization of 5-amino-4H-1,2,4-triazole-3-thiol (ATT) to form a poly-ATT (PATT) film for the selective and sensitive detection of Hg2+ ions by Anodic Stripping Voltammetry (ASV). The porous PATT film was uniformly coated on the surface through disulfide (SS) linkage, free NH, and amide bonds for binding preconcentrated Hg2+ ions. The prepared PATT@ASPE was characterized by cyclic voltammetry, Field-Emission Scanning Electron Microscopy (FE-SEM), Transmission Electron Microscopy (TEM) with Energy Dispersive X-ray spectroscopy (EDS) and Attenuated Total Reflection Infrared Spectroscopy (ATR-IR). Under optimized experimental conditions (0.1 M KCl as supporting electrolyte and preconcentration at –0.1 V for 120 s), PATT@ASPE was successfully used for detecting Hg2+. A linear relationship between the anodic peak current and [Hg2+] was achieved in the concentration range of 0.03 to 245 nM, with a limit of detection (S/N = 3) of 0.005 nM and a calculated sensitivity of 15.0085 µAnM−1L-1 cm−2. Further, selective detection of Hg2+ was demonstrated in the presence of interfering species such as other heavy metal ions (Pb2+, Cd2+, Cu2+, etc.), organic molecules, other cations, and various anions. The electroanalytical performance of PATT@ASPE exhibited outstanding long-term stability and reproducibility. Finally, PATT@ASPE was successfully applied to measure Hg2+ in fish muscle samples, and the results were validated using inductively coupled plasma-mass spectrometry.

Combined Effect of Ultrasound and Low-Heat Treatments on E. coli in Liquid Egg Products and Analysis of the Inducted Structural Alterations by NIR Spectroscopy.

In this study, sonication with mild heat treatment was used to reduce the E. coli count in inoculated liquid whole egg, egg yolk and albumen. Ultrasonic equipment (20/40 kHz, 180/300 W) has been used for 30/60 min with a 55 °C water bath. The combination of sonication and low-heat treatment was able to reduce the concentration of E. coli from 5-log CFU × mL-1 below 10 CFU × mL-1 at 300 W, 40 kHz and 60 min of sonication in liquid egg products. The 60 min treatment was able to reduce the E. coli concentration below 10 CFU × mL-1 in the case of egg yolk regardless of the applied frequency, absorbed power or applied energy dose. The 30 min treatment of sonication and heating was able to reduce significantly the number of E. coli in the egg products, as well. Our results showed that sonication with mild heat treatment can be a useful technique to decrease the number of microorganisms in liquid egg products to a very low level. Near-infrared spectroscopy was used to investigate structural changes in the samples, induced by the combined treatment. Principal component analysis showed that this method can alter the C-H, C-N, -OH and -NH bonds in these egg products.

Plasma-Induced Graft Polymerization of Polyethylenimine onto Chitosan/Polycaprolactone Composite Membrane for Heavy Metal Pollutants Treatment in Industrial Wastewater

The present study manifests an innovative and green approach to graft metal ion adsorbent, polyethylenimine (PEI), onto an electrospun chitosan (CS)/polycaprolactone (PCL) composite membrane via atmospheric pressure nitrogen plasma grafting polymerization. FTIR absorption peak at around 1690 cm−1 was attributed to the bending vibration of N-H from PEI. Since the plasma exposure time is a dependent factor of –NH bond formation, an increased nitrogen content up to 3.3% was observed with an extensive reaction time under plasma treatment. In addition, N1s spectra showed a clear PEI dominating characteristic at 401.7 eV, which suggested a successful grafting of PEI onto the CS/PCL membrane. According to the EDX analysis, a significant amount of copper ions was detected in PEI-CS/PCL membranes. This study showed that a greener wastewater treatment can be realized with the developed plasma synthesis technology.

High N‐H Photoacidity of a Nitrogen‐Rich Fused Ring Heteroaromatic Scaffold

AbstractIt is shown that 4‐methyl‐7‐(4‐nitrophenyl)‐triazolo[3,2‐c]triazole exhibits a high photoacidity, unprecedented in neutral molecules in which the proton is delivered by a NH bond, which promotes acetalization of aldehydes under irradiation by a near‐UV low power LED. Time dependent transient absorption spectroscopy shows a series of stimulated emission signals attributable to photo‐tautomerization and formation of the deprotonated species, followed by broad positive absorption band which does not decay within the investigated timescale, compatible with the formation of a long living species, possibly the anion in the lowest energy triplet state. Computational analyses qualitatively confirm the strong photoacidity of the molecule in all its tautomeric forms, allow to assign transient absorption signals, and show that the first singlet excited state exhibits high spin‐orbit couplings with excited triplet states which could promote a fast singlet‐triplet transition, thus leading to a long living species able to photocatalyze chemical reactions.

Detection of heavy metal ion in real samples with fiber based paper based on new rare earth cluster

Chromium (Cr) is an important material, but also one of the most toxic heavy metal pollutants, showing great threat to human health and ecological environment, thus, accurate and rapid detection of Cr3+ has far-reaching significance. In this work, based on the ligand of 2,3,4,5,6-pentafluorobenzoic acid (HPFBA) that does not contains oscillation effect group such as “CH, OH, and NH bond”, three rare earth dinuclear cluster of Ln2(PFBA)6(phen)2(H2O)2 (Ln = Tb3+1-Tb, Eu3+1-Eu, Gd3+1-Gd, phen = 1,10-phenanthroline) were obtained. 1-Tb shows excellent stability and luminescence properties. In depth investigation reveals that 1-Tb shows quick detection towards Cr3+ in water through luminescence “turn-off”, with extremely short response time of 1.0 min, very low limit of detection (LOD) of 5.2 ppb and no interference from other ions. The LOD value is much lower than the total content of chromium for water in China (15 ppm, GB9078-1996). In the actual environment such as tap water, lake water, human, and serum, 1-Tb shows excellent detection and recovery rate for Cr3+. More interestingly, a fiber based paper of test paper that based on 1-Tb and ordinary filter paper was fabricated, which can probe Cr3+ by visible color changes to the naked eye under UV light.

Removal trends of typical priority control pollutants in wastewater treatment plant tailwater: Mechanisms clarifying and optimal process selection

Priority control pollutants (PCPs) have attracted much attention due to their safety concerns during effluent recycling in wastewater treatment plants (WWTPs). To clarify the removal characteristics of typical PCPs in WWTP effluent, the removal rates of eight typical PCPs during coagulation, ozonation, ultrafiltration (UF) and their combined processes were investigated. Experimental results revealed that single advanced treatment could not efficiently remove all PCPs within the WWTP effluent, whereas the combined processes significantly improved the removal rates due to the synergy of different treatment units. Specifically, ATZ exhibited the highest removal efficiency of 72.45 % when the coagulation-ozonation progressed, owing to the strong attacking of ozone onto the reactive groups (CC bond, aniline, amido group). Similarly, >93.4 % of SMZ, DCF, NaP, and Ant were efficiently removed during the ozonation-UF treatment. By contrast, adsorption by membrane was the main reason for the excellent removal of BaA (95.32 %) during ozonation-UF process and BaP (96.28 %) in coagulation-UF treatment. The optimized selective strategies for different treatment processes for the above-mentioned eight PCPs reduction were proposed based on analytical hierarchical processes, and the simulation results revealed that: ozone oxidation and UF process were more feasible for the tertiary treatment of PCPs characterized by two rings linked by NH bonds, as well as those PAHs with three or more benzene rings; whereas coagulation-ozone and coagulation-UF were for PCPs with triazine rings and monocyclic aromatic compounds with carboxyl groups.

Synthesis, molecular structure, conformational, and intramolecular hydrogen bond strength of ethyl 3-amino-2-butenoate and its N-Me, N-Ph, and N-Bn analogs; An experimental and theoretical study

Amino derivatives of ethyl acetoacetate like ethyl (Z)- 3-(amino)but-2-enoate (EAB), ethyl (Z)- 3-(methylamino)but-2-enoate (Me-EAB), ethyl (Z)- 3-(phenylamino)but-2-enoate (Ph-EAB), and ethyl (Z)- 3-(benzylamino)but-2-enoate (Bn-EAB) were synthesized. Their structures, conformations, and intramolecular hydrogen bonding (IHB) is characterized using computational analysis (density functional theory, DFT, methods) at the B3LYP/6-311++G(d,p) level and spectroscopic techniques)IR, UV, and NMR). All the mentioned theoretical and experimental results were compared to those of (Z)-methyl 3-aminobut-2-enoate (MAB). The vibrational spectra of EAB are fully assigned. Vibrational spectroscopy results confirmed the existence of two conformers of title molecules. DFT calculations at the B3LYP/6-311++G(d,p) level show the calculated NH bond lengths in EAB, Me-EAB, Ph-EAB, Bn-EAB, and MAB are 1.015, 1.017, 1.022, 1.018, and 1.014 Ǻ, respectively. Also, according to the natural bond orbital (NBO) results, the σN-H10↔LP(2)O7 interactions for EAB, Me-EAB, Ph-EAB, Bn-EAB, and MAB are 5.21, 6.77, 8.65, 7.18, and 5.11 kcal/mol, respectively. So, the trend in IHB strength is: Ph-EAB > Bn-EAB ∼ Me-EAB > EAB ∼ MAB, which also agrees with the mentioned experimental results. The mentioned trend also is confirmed by the LP(O7)↔σNH steric exchange interaction.

Nitrogen-rich based conjugated microporous polymers for highly efficient adsorption and removal of COVID-19 antiviral drug chloroquine phosphate from environmental waters

Chloroquine phosphate (CQP) has been suggested as an important and effective clinical reliever medication for the 2019 coronavirus (COVID-19). Nevertheless, its excessive use will inevitably cause irreparable damage to the entire ecosystem, thereby posing a considerable environmental safety concern. Hence, the development of highly-efficient methods of removing CQP from water pollution sources, e.g., effluents from hospitals and pharmaceutical factories is significant. This study reported the fabrication of novel CN bond linked conjugated microporous polymers (CMPs) (BPT–DMB–CMP) with multiple nitrogen-rich anchoring sites for the quick and efficient removal of CQP from aqueous solutions. The irreversible covalent CN bond linked in the internal framework of BPT–DMB–CMP endowed it with good chemical stability and excellent adsorbent regeneration. With its predesigned functional groups (i.e., rich NH bonds, triazine rings, and benzene rings) and large area surface (1,019.89 m2·g−1), BPT–DMB–CMP demonstrated rapid adsorption kinetics (25 min) and an extraordinary adsorption capacity (334.70 mg·g−1) for CQP, which is relatively higher than that of other adsorbents. The adsorption behavior of CQP on BPT–DMB–CMP corresponded with Liu model and mixed-order model. Based on the density functional theory (DFT) calculations, X-ray photoelectron spectroscopy (XPS), and adsorption comparisons test, the halogen bonding, and hydrogen bonding cooperates with π − π, C H···π interactions and size-matching effect in the CQP adsorption system on BPT–DMB–CMP. The excellent practicability for the removal of CQP from real wastewater samples verified the prospect of practical application of BPT–DMB–CMP. BPT–DMB–CMP exhibited the application potentials for the adsorption of other antiviral drugs. This work opens up an efficient, simple, and high adsorption capacity way for removal CQP.

Soybean protein isolate treated with transglutaminase (TGase) enhances the heat tolerance of selected lactic acid bacteria strains to spray drying

TGase treated soy protein isolate (SPI) was confirmed to improve the survival of Lb. bulgaricus CICC 6047 subjected to spray drying. The viability of this strain increased from 70.69 % to 86.01 % due to elevating thermal stability. The smoother bacterial cell surface was observed by TGase treated SPI. TGase treatment changed the secondary conformation of SPI, having α-helical structure increased. Chemical bonds (hydrogen bond, CN bond, NH bond) proved the enzyme-modified SPI to have enhanced resistance to heat. The addition of TGase treated SPI allowed other LAB strains to tolerate the spray drying better. Their survival percentage after spray drying was 83.44 % for Le. mesenteroides CICC 6055, 80.64 % for Lb. acidophilus NCFM, 87.79 % for B. animalis BI-03 and 87.02 % for Lb. plantarum CICC 6009, respectively. The good survival of the selected LAB strains from TGase treated SPI powders was observed during storage of 8 weeks at 4 °C.

Terminal and Super‐Basic Parent Imides of Hafnium

AbstractA dinuclear hafnium complex containing the parent imido ligand [(PN)(PNC)Hf=NH{μ2‐K}]2 (2) (PN−=(N‐(2‐PiPr2‐4‐methylphenyl)‐2,4,6‐Me3C6H2; PNC2−=(N‐(2‐PiPr2‐4‐methylphenyl)‐2,4,6‐CH2Me2C6H2), was prepared by reduction of the bisazide trans‐[(PN)2Hf(N3)2] (1) with two equiv of KC8. Encapsulation of K+ in 2 with crown‐ether or cryptand affords the first discrete salt [K(encap)][(PN)(PNC)Hf≡NH] (encap=18‐crown‐6(THF)2, 3; 2,2,2‐Kryptofix, 4), featuring a terminal parent imide and possessing some of the shortest Hf−N bond lengths known to date. DFT calculations revealed formation of 2 to proceed via an extremely basic monomeric nitrido, [(PN)2Hf≡N]−(A), having a computed pKBH+ of ∼57 followed by heterolytic splitting of an inert 1,2‐CH bond of a benzylic methyl group across the Hf≡N triple bond in A. An electronic structure analysis reveals A to possess a covalent Hf≡N triple bond and of super‐basic character. We also showcase reactivity of the Hf≡NH bond with various electrophiles.