Hydride Groups Research Articles

In Situ Monitoring of Allylamine and 1,1,3,3-Tetramethyldisiloxane Reaction to Form 2,2,7,7-Tetramethyl-1-oxa-3-aza-2,7-disilacycloheptane Using Raman Spectroscopy

The cyclic siloxazane, i.e., 2,2,7,7-tetramethyl-1-oxa-3-aza-2,7-disilacycloheptane (1), is a useful industrial intermediate that is challenging to produce. One method to synthesize 1 is through concurrent dehydrocoupling and hydrosilylation reactions between 1 and allylamine. This chemistry is highly exothermic and also generates a significant amount of H2. Raman spectroscopy was demonstrated to be an effective analytical method to track both reactions. It enables a safe reaction scale-up by monitoring the consumption of allyl groups and the silicon hydride (SiH) groups. Both functional groups could be readily quantified by using a solvent as an internal standard. It is found that the observed SiH signal can be attributed to an intermediate species, which would undergo a relatively slower hydrosilylation reaction. Interesting kinetics behavior is observed that leads to a mechanistic understanding of the catalyst's role in catalyzing the two elementary steps. The ability to track these moieties is critical to the development of a safe process that avoids accumulation of SiH intermediates.

Chemical diversity in angiosperms - monoterpene synthases control complex reactions that provide the precursors for ecologically and commercially important monoterpenoids.

Monoterpene synthases (MTSs) catalyze the first committed step in the biosynthesis of monoterpenoids, a class of specialized metabolites with particularly high chemical diversity in angiosperms. In addition to accomplishing a rate enhancement, these enzymes manage the formation and turnover of highly reactive carbocation intermediates formed from a prenyl diphosphate substrate. At each step along the reaction path, a cationic intermediate can be subject to cyclization, migration of a proton, hydride, or alkyl group, or quenching to terminate the sequence. However, enzymatic control of ligand folding, stabilization of specific intermediates, and defined quenching chemistry can maintain the specificity for forming a signature product. This review article will discuss our current understanding of how angiosperm MTSs control the reaction environment. Such knowledge allows inferences about the origin and regulation of chemical diversity, which is pertinent for appreciating the role of monoterpenoids in plant ecology but also for aiding commercial efforts that harness the accumulation of these specialized metabolites for the food, cosmetic, and pharmaceutical industries.

Noble gas hydrides: theoretical prediction of the first group of anionic species.

The first group of anionic noble-gas hydrides with the general formula HNgBeO- (Ng = Ar, Kr, Xe, Rn) is predicted through MP2, Coupled-Cluster, and Density Functional Theory computations employing correlation-consistent atomic basis sets. We derive that these species are stable with respect to the loss of H, H-, BeO, and BeO-, but unstable with respect to Ng + HBeO-. The energy barriers of the latter process are, however, high enough to suggest the conceivable existence of the heaviest HNgBeO- species as metastable in nature. Their stability arises from the interaction of the H- moiety with the positively-charged Ng atoms, particularly with the σ-hole ensuing from their ligation to BeO. This actually promotes relatively tight Ng-H bonds featuring a partially-covalent character, whose degree progressively increases when going from HArBeO- to HRnBeO-. The HNgBeO- compounds are also briefly compared with other noble-gas anions observed in the gas phase or isolated in crystal lattices.

Effect of surface modification of nanosilica by hydride-groups on morphology, strength and resistance of epoxy-composites

A chemical modification of fumed silica surface by active groups can enlarge its functional capabilities as a polymer filler. As a result, a new possibility in the formation of reinforced polymeric composites appears.In this work, silica with grafted silicon hydride (≡Si–H) groups was found to be active in the processes of hydrosilylation of active bonds in monomers during their polymerization. Hydride-silylated silica was obtained via his treatment with triethoxysilane. The presence of grafted silicon hydride groups was confirmed by means of IR spectroscopy, and their concentration measured by titrimetric and spectrophotometric analysis was found to be about 0.4 mmol/g. Silica-epoxy composites were prepared and the resulted materials after curing were subject to compression, bending, micro-hardness and adhesion mechanical tests.According to experimental results, the synthesized hydride-silica fillers let to enhance the important strength properties of the epoxy-polymer already at 2 wt% loading. In particular, the elastic modulus for compression increased by 30–40%, the one for bending – by 1.2–1.5 times, the flexural strength – by 1.5–2 times, and adhesion to steel – by 2.5–2.8 times. These effects are achieved due to good compatibility and homogeneous distribution of the filler in the resin, as shown by SEM microscopy (after hydride-modification, the silica agglomerates in epoxy disappear). IR-spectroscopy shows a possible increasing of epoxy conversion's rate after 2%-filling by hydride-silica. Thus, preliminary results indicate that fumed silica with grafted silicon hydride groups shows promise as active reinforcing filler for epoxy polymers.The work demonstrates the potential of nanosilica filler surface hydride-silylation for low-cost strengthening of epoxy polymers for industry and repair.

Nickel-Catalyzed Hydroamination and Hydroalkoxylation of Enelactams with Unactivated Amines and Alcohols.

Nickel-catalyzed hydroamination and hydroalkoxylation of enelactams with unactivated amines and alcohols are reported. This method showed good functional group tolerance and delivered the corresponding hydrofunctionalized products in good to excellent yields (≤98%). Furthermore, an intramolecular hydroalkoxylation of an enelactam was also realized, giving a cyclization product in a good yield. Mechanistic studies indicated that tBuI acts as a hydride donor and radical precursor, which is crucial for the success of the reaction.

Dinuclear and tetranuclear group 10 metal complexes constructed from linear tetrasilane comprising both Si-H and Si-Si moieties

The activation of Si-H bonds and/or Si-Si bonds in organosilicon compounds by transition-metal species plays a crucial role for the production of functional organosilicon compounds. Although group-10-metal species are frequently used to activate Si-H and/or Si-Si bonds, so far, systematic investigation to clarify the preferences of these metal species with respect to the activation of Si-H and/or Si-Si bonds remain elusive. Here, we report that platinum(0) species that bear isocyanide or N-heterocyclic-carbene (NHC) ligands selectively activates the terminal Si-H bonds of the linear tetrasilane Ph2(H)SiSiPh2SiPh2Si(H)Ph2 in a stepwise manner, whereby the Si-Si bonds remain intact. In contrast, analogous palladium(0) species are preferably inserted into the Si-Si bonds of the same linear tetrasilane, whereby the terminal Si-H bonds remain intact. Substitution of the terminal hydride groups in Ph2(H)SiSiPh2SiPh2Si(H)Ph2 with chloride groups leads to the insertion of platinum(0) isocyanide into all Si-Si bonds to afford an unprecedented zig-zag Pt4 cluster.

Biologically inspired 3Fe4S cluster as structural mimics of FeMoco M‐cluster

AbstractA 3Fe4S cluster related to M‐cluster of Mo‐nitrogenase is reported. [K(THF)5][Fe3(μ‐bdt)2(μ‐PPh2)(CO)5] (1) is synthesized from photo‐assisted structural rearrangement of [K(THF)2][(μ,κ2‐bdt)Fe2(μ‐PPh2)(CO)5] under visible light irradiation. The molecular structure of 1 consists of a Fe3 core bearing one dithiolate bridge and the second dithiolate group capping onto the metallic plane. The structural motif of 1 is analogous to that of Mo‐participated 3Fe4S unit in M‐cluster of Mo‐nitrogenase, with the similar Fe‐Fe and Fe‐S bond distances. Upon protonation in 193 K, a Fe‐hydride species (1H) is generated and characterized to possess the bridging hydride group (δ = −12.57 ppm) by 1H‐NMR spectroscopy and DFT calculation. In CH3CN solution, complex 1 exhibits a reversible reduction and oxidation process at = −1.94 V and = −0.18 V, respectively, at 273 K. The reduction behavior of 1 in CH2Cl2 solution at 243 K displays a slight modification in the presence of trifluoroacetic acid, revealing a moderate anodic potential shift (~50 mV). The current amplitude of the reduction wave is linearly increased with the increasement of acid added, indicative of the catalytic event.

Nickel-Catalyzed Remote C(sp3)–N/O Bond Formation of Alkenes with Unactivated Amines and Alcohols

Transition metal-catalyzed remote hydrofunctionalization of alkenes is an efficient method to realize C(sp3)–H functionalization. However, remote hydrofunctionalization of alkenes with unactivated amines and alcohols has not been successfully developed to date. Herein, we report an efficient nickel-catalyzed remote hydroamination and hydroetherification of alkenes with unactivated amines and alcohols, accessing a series of gem-diamine and N,O-acetal derivatives in good to high yields (up to 93%) and exclusive regioselectivities. The mechanistic investigations and DFT computations indicated that the use of 2-iodo-2-methylpropane (tBuI) as both a mild hydride source and radical precursor was essential to afford the remote functionalized products. This research work provides an efficient method to install an amino or alkoxyl group at the C(sp3)–H position that is far from the double bond of alkenes.

Solid state lithium-ion rechargeable batteries: An overview

Rechargeable solid-state Li-ion batteries have potential for applications in mobile devices and electric vehicles in the near future to meet the growing demand for high energy storage. Research on rechargeable solid-state Li-ion batteries has a long history and has been accelerating recently. Solid electrolytes are the most important component in the all-solid-state batteries. Solid electrolytes can be divided into the following groups: oxide groups (Perovskite Li3.3La0.56TiO3, NASICON LiTi2(PO4)3, LISICON Li14Zn(GeO4)4, and Li7La3Zr2O12 garnets), sulfide groups (Li2S – P2S5 and Li2S – P2S5 – MxS), hydride group (LiBH4, LiBH4–LiX (X=Cl, Br or I), LiBH4–LiNH2, LiNH2, Li3AlH6 and Li2NH), halogen group (LiI, spinel Li2ZnI4 and anti-perovskite Li3OCl), and polymer group (mainly polyethylene). Although electrolytes with good ionic conductivity have been used, the performance of solid-state rechargeable Li-ion batteries is still far behind that of the ones using liquid electrolytes. Along with the development of science and technology, many scientific and technical problems in solid-state rechargeable Li-ion batteries have been discovered. In this review, the major issues of solid-state rechargeable Li-ion batteries will be breifly documented: the interface between the active material (AM) and the solid electrolyte (SE), aging of the solid-solid interface, electrode structure, and fabrication methods.

Site-selective radical reactions of kinetically stable open-shell singlet diradicaloid difluorenoheteroles with tributyltin hydride and azo-based radical initiators.

We have demonstrated site-selective radical reactions of the kinetically stable open-shell singlet diradicaloids difluoreno[3,4-b:4',3'-d]thiophene (DFTh) and difluoreno[3,4-b:4',3'-d]furan (DFFu) with tributyltin hydride (HSn(n-Bu)3) and azo-based radical initiators. Treatment of these diradicaloids with HSn(n-Bu)3 induces hydrogenation at the ipso-carbon in the five-membered rings, while treatment with 2,2'-azobis(isobutyronitrile) (AIBN) induces substitution at the carbon atoms in the peripheral six-membered rings. We have also developed one-pot substitution/hydrogenation reactions of DFTh/DFFu with various azo-based radical initiators and HSn(n-Bu)3. The resulting products can be converted into substituted DFTh/DFFu derivatives via dehydrogenation. Theoretical calculations unveiled a detailed mechanism of the radical reactions of DFTh/DFFu with HSn(n-Bu)3 and with AIBN, and that the site-selectivity of these radical reactions is controlled by the balance of the spin density and the steric hindrance in DFTh/DFFu.

High-level quantum chemistry exploration of reduction by group-13 hydrides: insights into the rational design of bio-mimic CO2 reduction

In the present study, we have used computational quantum chemistry to explore the reduction of various types of substrates by group-13 hydrides. We use the high-level L-W1X method to obtain the energies for the constituent association and hydride transfer reactions. We find that the hydride transfer reactions are highly exothermic, while the preceding association reactions are less so. Thus, improving the thermodynamics of substrate association may improve the overall process. Among the various substrates, amine and imine show the strongest binding, while CO2 shows the weakest. Between the group-13 hydrides, alanes bind most strongly with the substrates, and they also have the most exothermic hydride transfer reactions. To facilitate CO2 binding, we have examined alanes with electron-withdrawing groups, and we indeed find CF3 groups to be effective. Drawing inspiration from the RuBisCO enzyme for CO2 fixation, we have further examined the activation of CO2 with two independent AlH(CF3)2 molecules, with the results showing an even more exothermic association. This observation may form the basis for designing an effective dialane reagent for CO2 reduction. We have also assessed a range of lower-cost computational methods for the calculation of systems in the present study. We find the DSD-PBEP86 double-hybrid DFT method to be the most suitable for the study of related medium-sized systems.

Plasma Functionalization of Silica Bilayer Polymorphs.

Ultrathin silica films are considered suitable two-dimensional model systems for the study of fundamental chemical and physical properties of all-silica zeolites and their derivatives, as well as novel supports for the stabilization of single atoms. In the present work, we report the creation of a new model catalytic support based on the surface functionalization of different silica bilayer (BL) polymorphs with well-defined atomic structures. The functionalization is carried out by means of in situ H-plasma treatments at room temperature. Low energy electron diffraction and microscopy data indicate that the atomic structure of the films remains unchanged upon treatment. Comparing the experimental results (photoemission and infrared absorption spectra) with density functional theory simulations shows that H2 is added via the heterolytic dissociation of an interlayer Si-O-Si siloxane bond and the subsequent formation of a hydroxyl and a hydride group in the top and bottom layers of the silica film, respectively. Functionalization of the silica films constitutes the first step into the development of a new type of model system of single-atom catalysts where metal atoms with different affinities for the functional groups can be anchored in the SiO2 matrix in well-established positions. In this way, synergistic and confinement effects between the active centers can be studied in a controlled manner.

Theoretical Study for Evaluating and Discovering Organic Hydride Compounds as Potential Novel Methylation Reagents.

Methylation reaction is a fundamental chemical reaction that plays an important role in the modification of drug molecules, DNA, as well as proteins. This work focuses on seeking potential novel methylation reagents through a systematic investigation of the thermodynamics and reactivity of methyl-substituted organic hydride radical cations (XH•+s). In this work, 45 classical and important XH•+s were designed to investigate the relationship between their structure and reactivity, to find excellent or potential methylation reagents. The Gibbs free energy and activation free energy of XH•+ to release the methyl radical in MeCN at 298.15 and 355 K are calculated with the density functional theory (DFT) method to quantitatively measure the reactivity of XH•+ as a methylation reagent in this work. The relationships between structures and reactivities on XH•+s as methylation reagents are well examined. Since we have calculated the Gibbs free energy and activation free energy of trifluoromethyl-substituted organic hydride compound radical cations (X′H•+) releasing trifluoromethyl radicals in MeCN with the DFT method in our previous work, accordingly, the relationship of thermodynamics and reactivity between X′H•+ releasing trifluoromethyl radical and XH•+ releasing methyl radical is discussed in detail. Excitingly, 4 XH•+s (1H•+, 3H•+∼4H•+, and 44H•+) are found to be excellent methyl radical reagents, while 9 XH•+s (5H•+, 6H•+, 9H•+, 10H•+, 12H•+, 13H•+, 15H•+, 43H•+, and 45H•+) are found to be potential methyl radical reagents in chemical synthesis. The molecular library and reactivity database of novel methylation reagents could be established for synthetic chemists to query and use. Our work may offer a theoretical basis and reference experience for screening different substituted organic hydride compounds (YRHs) as alkylation reagents.

In English

Fumed silica has found widespread application in industry due to variety of fascinating properties. Owing to its specific manufacturing process, it consists of finely dispersed particles and is featured with large specific surface area covered by profoundly reactive silanol groups which are available for chemical grafting. Spherical shape of fumed silica particles and lacking porosity provides a space-filling structure. These characteristics implement the fume silica’s utilization as high-surface-area carriers for various catalysts, i.e. metallic nanometer-sized particles, organic moieties, etc. Currently a great attention is called to on-surface grafting to improve the silica-based carrier. Most of research is carried out in area of liquid phase chemistry involving an abundance of expensive and often toxic solvents while the space-filling properties of silica are favoring reactions in fluidized bed conditions. In current research fumed silica (A-300) was a subject for hydridesilylation with triethoxysilane under fluidized bed conditions. In all synthesis reported in current research the insignificant amount of solvent (1.00 wt. % of the amount used in typical wet-chemical modifications method) was spent for the silica surface silylation. While the mass ratio of silica/TES was kept constant, other conditions, i.e. solvent/catalyst presence, surface pretreatment, additional treatment with water, and the fluidized bed heating mode have been varied. FTIR spectroscopy revealed the interaction between groups of triethoxysilane and silica surface silanol groups and demonstrated the effect of modification conditions on the density of the hydridesilyl groups coverage. The results of FTIR spectroscopic studies have confirmed the presence of grafted silicon hydride groups on the surface of modified silica, as well as the presence of ethoxy and/or silanol groups – either intact or formed due to hydrolysis of the ethoxy groups. Titrimetric and spectrophotometric analysis was performed to estimate the concentration of grafted SiH groups (in all samples prepared under fluidized bed conditions their concentration ranged within about 0.28–0.55 mmol/g as dependent on the reaction conditions). Other important aspects of fluidization such as the presence of solvent and/or hydrolyzing agent, bed heating mode and the effect of the silica sample thermal pre-treatment are also discussed.

Aryl‐group substituted polysiloxanes with high‐optical transmission, thermal stability, and refractive index

AbstractPolysiloxanes are an important class of polymers for optoelectronic applications. Novel polysiloxanes with high‐refractive index (RI) based on phenanthrenyl‐substituted monomers are prepared by a polycondensation reaction starting from various substituted dialkoxysilanes as monomers. The substitution patterns on the Si atom are systematically changed to vary the properties of the linear polymers as well as the final cured material. The two monomers with polycyclic aromatic side groups 9‐phenanthrenylmethyldimethoxysilane and 9‐phenanthrenylphenyldimethoxysilane are synthesized and fully characterized, including their single crystal X‐ray structures. Linear polysiloxanes with variations in hydride, methyl, vinyl, phenyl, and phenanthrenyl side group content are prepared by acid‐ and base‐catalyzed polycondensation reactions. Both SiH and Si vinyl substituted polymers with molecular weights up to 30 kDa and adjustable RI's from 1.52 to 1.63 are obtained and the thermally cured by Pt‐catalyzed hydrosilylation reactions. Polysiloxane resins are obtained with high‐RI's, optical transmittance above 95% and thermal stabilities up to 420°C. Long‐term thermal stability tests show transmittance values above 85% even after 60 days of thermal treatment at 180°C.

Functionalization of biosourced silica and surface reactions with mercury in aqueous solutions

This study presents the production of pure silica from rice husk and its stepwise functionalization with triethoxysilane (TES) and silver nanoparticles. The derived TES-SiO2 (0.97 mmol TES per g of SiO2) and Ag0@SiO2 (3.70–21.60 mg Ag per g of SiO2) materials were used for the removal of Hg2+ from aqueous solutions in the presence of chloride ions. The removal of Hg2+ was rapid and the equilibrium solid phase loading was between 21 and 101 mg/g. TES-SiO2 was more effective than Ag0@SiO2 in removing mercury due to the highly reactive hydride groups. In the case of Ag0@SiO2 samples the removal of Hg2+ is proportional to the amount of Ag0. The materials were characterized before and after the removal of Hg2+ to allow insights into the interaction mechanism. The reaction products for TES-SiO2 sample were calomel (Hg2Cl2) and AgCl. On the surface of Ag0@SiO2 samples besides these products the silver amalgams Ag1.1Hg0.9 and possibly Ag2Hg3 were identified. These results show that redox reactions between silicon-hydride group, Ag0 and Hg2+ take place on the surface of the materials. The coexistence of calomel and silver amalgams on amorphous silica is observed for the first time while the calomel formation in heterogeneous Hg2+ redox systems is a rare observation. Also, the samples showed extraordinary efficiency in terms of Hg:Ag molar ratio (2.28–3.02), considerably higher than those reported before. Besides the beneficial effect of the Cl- presence on the removal of Hg2+ from the solution there is evidence of a hyperstoichiometric interaction between Ag0 and Hg2+ at the nanoscale.

Photopatterning of PDMS Films: Challenging the Reaction between Benzophenone and Silicone Functional Groups.

Direct photopatterning of PDMS (Polydimethylsiloxane) through benzophenone photo-inhibition has received great interest in recent years. Indeed, the simplicity and versatility of this technique allows for easy processing of micro-canals, or local control of PDMS mechanical properties. Surprisingly, however, the chemical reactions between silicone hydride and/or silicone vinyl groups and benzophenone have only been assessed through qualitative methods (e.g., Attenuated total reflection fourier transform infrared). In this communication, the previously proposed reaction pathways are challenged, using nuclear magnetic resonance (NMR) spectroscopy and size exclusion chromatography (SEC) monitoring. A different mechanism depicting the role of benzophenone irradiation on the polyaddition reaction of silicone formulations is proposed, and a simplified procedure involving aromatic solvent is finally disclosed.

In English

Fumed silica (FS) is widely used in numerous fields of application, the plastics industry being one of the most significance, where FS has proved to be successful as an efficient thickening, thixotropic, and anti-settling agent, as well as reinforcing filler. Chemical modification of silica surface enlarges its functional capabilities. In particular, silica with grafted silicon hydride groups was found to be active in the processes of hydrosilylation of alkene and alkyne bonds in monomers during their polymerization, resulting in the formation of reinforced polymeric composites. Recently, specific epoxy resins have gained significance, and FS was found to be useful, particularly as rheological additive. The aim of this study was to evaluate the efficiency of hydride-silylated FS (HFS) as a potentially active reinforcing component for epoxy-based polymers. The activation energy for hydrosilylation of olefins is higher than that for ring-opening polymerization of epoxides, therefore, one may expect the latter process with participation of ≡SiH groups to proceed more readily. HFS was obtained via FS treatment with triethoxysilane. The presence of grafted silicon hydride groups was confirmed by means of IR spectroscopy, and their concentration measured by titrimetric and spectrophotometric analysis was found to be about 0.4 mmol/g. FS-epoxy and HFS-epoxy composites were prepared by the corresponding filler introduction (2 wt. % loading) into the mixture of epoxy monomer and amine hardener. The resulted materials after curing were subject to compression, bending, and adhesion tests. Compression tests revealed that filling with FS and HFS reduced the compressive strength by 10%, however, HFS-epoxy composite was found to possess an increased by 20 % Young’s modulus for compression as compared to that for the unfilled epoxy polymer. Upon this, 2 wt. % loading with silicas keeps the ductility of the polymer. Also, silica-containing epoxy polymers showed an improved bending strength and bending modulus, the former being two times higher for HFS-epoxy composite than that for the unfilled polymer. The adhesion to steel was found to increase by more than 2 times upon filling with silicas, HFS-epoxy composite being also superior as compared to the FS-epoxy one. Thus, preliminary results indicate that fumed silica with grafted silicon hydride groups shows promise as active reinforcing filler for epoxy polymers.

Investigation of structural and optical properties of zirconia dioxide nanoparticles by radiation and thermal methods

The X-ray diffraction (XRD) spectrum of the nano-ZrO2compound was drawn, the crystal structure was determined at room temperature and under normal conditions. Radiation-thermal decomposition of water on nanosized ZrO2in the temperature range of [Formula: see text]–673 K has been studied by Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. It has been shown that nanosized zirconium dioxide adsorbs water via the molecular and dissociative mechanisms. Intermediate products of the radiation-induced heterogeneous decomposition of water, namely, the molecular oxygen and hydrogen peroxide radical ions, zirconium hydride, and hydroxyl radicals have been detected. A comparative analysis of changes in the absorption bands (ABs) of molecular water and surface hydroxyl groups with temperature has been conducted, and the stimulating role of radiation in the radiation-thermal process of water decomposition has been revealed. With the participation of nano-ZrO2during the radiation-heterogeneous decomposition of water to reveal the role of unbalanced cargo carriers that play the role of energy carriers under the influence of gamma-quantities in nano-ZrO2and nano-[Formula: see text] systems paramagnetic centers, their origin and acquisition kinetics learned by the EPR method.

Submillimeter and Far-infrared Spectroscopy of Monodeuterated Amidogen Radical (NHD): Improved Rest Frequencies for Astrophysical Observations

Observations of ammonia in interstellar environments have revealed high levels of deuteration, and all its D-containing variants, including ND$_3$, have been detected in cold prestellar cores and around young protostars. The observation of these deuterated isotopologues is very useful to elucidate the chemical and physical processes taking place during the very early stages of star formation, as the abundance of deuterated molecules is highly enhanced in dense and cold gas. Nitrogen hydride radicals are key species lying at the very beginning of the reaction pathway leading to the formation of NH$_3$ and organic molecules of pre-biotic interest, but relatively little information is known about their D-bearing isotopologues. To date, only ND has been detected in the interstellar gas. To aid the identification of further deuterated nitrogen radicals, we have thoroughly re-investigated the rotational spectrum of NHD employing two different instruments: a frequency-modulation submillimetre spectrometer operating in the THz region and a synchrotron-based Fourier Transform infrared spectrometer operating in the 50-240 cm$^{-1}$ wavelength range. NHD was produced in a plasma of NH$_3$ and D$_2$. A wide range of rotational energy levels has been probed thanks to the observation of high $N$ (up to 15) and high $K_a$ (up to 9) transitions. A global analysis including our new data and those already available in the literature has provided a comprehensive set of very accurate spectroscopic parameters. A highly reliable line catalogue has been generated to assist archival data searches and future astronomical observations of NHD at submillimetre and THz regimes.