Exploring the Tl 2 H 2 potential energy surface: A comparative analysis with group 13 systems and experiment.

Thallium chemistry is experiencing unprecedented importance. Therefore, it is valuable to characterize some of the simplest thallium compounds. Stationary points along the singlet and triplet Tl 2 H 2 potential energy surface have been characterized. Stationary point geometries were optimized with the CCSD(T)/aug-cc-pwCVQZ-PP method. Harmonic vibrational frequencies were computed at the same level of theory while anharmonic vibrational frequencies were computed at the CCSD(T)/aug-cc-pwCVTZ-PP level of theory. Final energetics were obtained with the CCSDT(Q) method. Basis sets up to augmented quintuple-zeta cardinality (aug-cc-pwCV5Z-PP) were employed to obtain energetics in order to extrapolate to the complete basis set limits using the focal point approach. Zero-point vibrational energy corrections were appended to the extrapolated energies in order to determine relative energies at 0 K. It was found that the planar dibridged isomer lies lowest in energy while the linear structure lies highest in energy. The results were compared to other group 13 M 2 H 2 (M = B, Al, Ga, In, and Tl) theoretical studies and some interesting variations are found. With respect to experiment, incompatibilities exist.

Characterization of Germanium Nanoparticles from Arylgermanium Trihydrides.

Germanium is a promising basis for nanomaterials due to its low toxicity and valuable optical and electronic properties. However, germanium nanomaterials have seen little research compared to other group 14 elements due to unpredictable chemical behavior and high costs. Here, we report the dehydrocoupling of o-tolylgermanium trihydride to amorphous nanoparticles. The reaction is facilitated through reflux at 162 °C and can be accelerated with an amine base catalyst. Through cleavage of both H2 and toluene, new Ge-Ge bonds form. This results in nanoparticles consisting of crosslinked germanium with o-tolyl termination. The particles are 2-6 nm in size and have masses above approximately 3500 Da. The organic substituents are promising for further functionalization. Combined with strong absorption up to 600 nm and moderate solubility and air stability, there are numerous possibilities for future applications.

NHC-Stabilized Mixed Group 13/14/15 Element Hydrides.

The syntheses of novel N-heterocyclic carbene (NHC) adducts of group 13, 14 and 15 element hydrides are reported. Salt metathesis reactions between NaPH2 and IDipp ⋅ GeH2 BH2 OTf (1) (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) led to mixtures of the two isomers IDipp ⋅ GeH2 BH2 PH2 (2 a) and IDipp ⋅ BH2 GeH2 PH2 (2 b); by altering the reaction conditions an almost exclusive formation of 2 b was achieved. Attempts to purify mixtures of 2 a and 2 b by re-crystallization from THF afforded a salt [IDipp ⋅ GeH2 BH2 ⋅ IDipp][PHGeH2 BH2 PH2 BH2 GeH2 ] (4) that contains the novel anionic cyclohexyl-like inorganic heterocycle [PHGeH2 BH2 PH2 BH2 GeH2 ]- . In addition, the borane adducts IDipp ⋅ GeH2 BH2 PH2 BH3 (3 a) and IDipp ⋅ BH2 GeH2 PH2 BH3 (3 b) as even longer chain compounds were obtained from reactions of 2 a/2 b with H3 B ⋅ SMe2 and were studied by NMR spectroscopy. Accompanying DFT computations give insight into the mechanism and energetics associated with 2 a/2 b isomerization as well as their decomposition pathways.

Detection and Characterization of Hydride Ligands in Copper Complexes by Hard X-Ray Spectroscopy.

Transition metal complexes, particularly copper hydrides, play an important role in various catalytic processes and molecular inorganic chemistry. This study employs synchrotron hard X-ray spectroscopy to gain insights into the geometric and electronic properties of copper hydrides as potential catalysts for CO2 hydrogenation. The potential of high energy resolution X-ray absorption near-edge structure (HERFD-XANES) and valence-to-core X-ray emission (VtC-XES) is demonstrated with measurement on Stryker's reagent (Cu6H6) and [Cu3(µ3-H)(dpmppe)2](PF6)2 (Cu3H), alongside a non-hydride copper compound ICu(dtbppOH) (Cuy-I). The XANES analysis reveals that coordination geometries strongly influence the spectra, providing only indirect details about hydride coordination. The VtC-XES analysis exhibits a distinct signal around 8975 eV, offering a diagnostic tool to identify hydride ligands. Theoretical calculations support and extend these findings by comparing hydride-containing complexes with their hydride-free counterparts.

Exploring Spin-Orbit Effects in a [Cu6Tl]+ Nanocluster Featuring an Uncommon Tl-H Interaction.

Reaction of [CuH(PPh3)]6 with 1 equiv. of Tl(OTf) results in formation of [Cu6TlH6(PPh3)6][OTf] ([1]OTf]), which can be isolated in good yields. Variable-temperature 1H NMR spectroscopy, in combination with density functional theory (DFT) calculations, confirms the presence of a rare Tl-H orbital interaction. According to DFT, the 1H chemical shift of the Tl-adjacent hydride ligands of [1]+ includes 7.7 ppm of deshielding due to spin-orbit effects from the heavy Tl atom. This study provides valuable new insights into a rare class of metal hydrides, given that [1][OTf] is only the third isolable species reported to contain a Tl-H interaction.

Stabilisation of the [SiH6]2- Anion within a Supramolecular Assembly.

The hypercoordinate [SiH6]2- anion is not stable in solution. Here, we report the room temperature, solution stable molecular [SiH6]2- complex, [{KCa(NON)(OEt2)}2][SiH6] (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene)), where the [SiH6]2- anion is stabilised within a supramolecular assembly that mimics the solid-state environment of the anion in the lattice of K2SiH6. Solution-state reactivity of the complex towards carbon monoxide, benzaldehyde, azobenzene and acetonitrile is reported, yielding a range of reduction and C-C coupled products.

Synthesis and Reactivity of Discrete Europium(II) Hydride Complexes.

The bulky ß-diketiminate ligand frameworks [BDIDCHP]- and [BDIDipp/Ar]- (BDI=[HC{C(Me)2N-Dipp/Ar}2]- (Dipp=2,6-diisopropylphenyl (Dipp); Ar=2,6-dicyclohexylphyenyl (DCHP) or 2,4,6-tricyclohexylphyenyl (TCHP)) have been developed for the kinetic stabilisation of the first europium (II) hydride complexes, [(BDIDCHP)Eu(µ-H)]2, [(BDIDipp/DCHP)Eu(µ-H)]2 and [(BDIDipp/TCHP)Eu(µ-H)]2, respectively. These complexes represent the first step beyond the current lanthanide(II) hydrides that are all based on ytterbium. Tuning the steric profile of ß-diketiminate ligands from a symmetrical to unsymmetrical disposition, enhanced solubility and stability in the solution-state. This provides the first opportunity to study the structure and bonding of these novel Eu(II) hydride complexes crystallographically, spectroscopically and computationally, with their preliminary reactivity investigated.

Hydrogenolysis of Cationic Half-Sandwich Zinc Complexes Containing a Chelating Amine: Facile Cleavage of Zinc-Carbon Bond by Dihydrogen to Give Zinc Hydride Cations.

Cationic half-sandwich zinc complexes containing chelating amines [Cp*Zn(Ln)][BAr4 F] (2 a, Cp*=η3-C5Me5, Ln=N,N,N',N'-tetramethylethylenediamine, TMEDA; 2 b, Ln=N,N,N',N'-tetraethylethylenediamine, TEEDA; 2 c, Cp*=η1-C5Me5, Ln=N,N,N',N'',N''-pentamethyldiethylenetriamine, PMDTA; Ar4 F=(3,5-(CF3)2C6H3)4) reacted with dihydrogen (ca. 2 bar) in THF at 80 °C to give molecular zinc hydride cations [(Ln)ZnH(thf)m][BAr4 F] (3 a,b, m=1; 3 c, m=0) previously reported along with Cp*H. Pseudo first-order kinetics with respect to the concentration of 2 b suggests heterolytic cleavage of dihydrogen by the Zn-Cp* bond, reminiscent of σ-bond metathesis. Hydrogenolysis of the zinc cation 2 b in the presence of benzophenone gave the zinc alkoxide [(TEEDA)Zn(OCHPh2)(thf)][BAr4 F] (5 b). Cation 2 b was shown to catalytically hydrogenate N-benzylideneaniline. The PMDTA complex 2 c underwent C-H bond activation in acetonitrile to give a dinuclear µ-κC,κN-cyanomethyl zinc complex [(PMDTA)Zn(CH2CN)]2[BAr4 F]2 (6 c).

A Data-Driven Approach for Enhanced CO2 Capture with Ruthenium Complexes.

To attain carbon neutrality, significant efforts have been made to capture and utilize CO2. The homogeneous hydrogenation of CO2 catalyzed by transition metal complexes, particularly the ruthenium complexes, has demonstrated significant advantages and is regarded as a viable approach for practical application. Insertion of CO2 into the Ru-H bond, producing the Ru-formate product, is the key step in the hydrogenation of CO2. In order to parameterize the catalytic activities in the CO2 insertion into the Ru-H bond, the concept of simplified mechanism-based approach with data-driven practice (SMADP) has been introduced in this paper. The results showed that the hydricity of the Ru-H complex (ΔGH-) might serve as a single active descriptor in the process of CO2 insertion, and that a novel ruthenium complex in CO2 catalysis may not be easily obtained by mere modification of the auxiliary ligand at the ruthenium metal site.

Heat Capacity Function, Enthalpy of Formation and Absolute Entropy of Mg(AlH4 )2.

In this investigation, we set out first to characterize the thermodynamics of Mg(AlH4 )2 and secondly to use the determined data to reevaluate and update existing estimation procedures for heat capacity functions, enthalpies of formation and absolute entropies of alanates. Within this study, we report the heat capacity function of Mg(AlH4 )2 in the temperature range from 2 K to 370 K and its enthalpy of formation and absolute entropy at 298.15 K, being - 70 . 6 ± 3 . 6 ${ - 70.6 \pm 3.6}$  kJ mol-1 and 133.06 J (K mol)-1 , respectively. Using these values, we updated and expanded methods for the estimation of thermodynamic data of alanates.

Pt12H24 -: A Cuboctahedral Platinum Hydride Cluster Cage.

The platinum hydride cluster Pt12H24 - is studied in gas phase by a combination of trapped ion electron diffraction and density functional theory computations. We find a cuboctahedral platinum cage with bridge bound hydrogen atoms. This unusual structure is stabilized by Pt-H-Pt multicenter bonds and shows characteristics of spherical aromaticity.

Theoretical Description of Hydride-hydride Interactions in Selected Hydrogen Storage Materials.

In recent years there has been growing interest in the use of metal hydrides as hydrogen rich sources. The high content of hydride-hydride contacts Hδ-⋅⋅⋅δ-H in these materials appears to be relevant for hydrogen formation. At present time there is no consensus whether these contacts are attractive or repulsive. Accordingly, the main goal of this article is to shed light on physical factors which constitute homopolar hydride-hydride interactions Hδ-⋅⋅⋅δ-H in selected transition metal complexes i. e. HCoL4, L=CO,PPh3,PH3. In order to achieve this goal, the charge and energy decomposition ETS-NOCV approach along with the Interacting Quantum Atoms (IQA) and reduced density gradient (NCI) are applied for the bonded adducts L4CoH⋅⋅⋅HCoL4. Based on DFT and correlated methods it has been shown, contrary to classical interpretations, that hydride-hydride interactions might be attractive and even far stronger than classical hydrogen bonds. The stability of the adducts is increased by phosphine ligand installation: overall Hδ-⋅⋅⋅δ-H bonding energy changes in the order: CO≪PPh3~PH3. It has been revealed that depending on monomer's conformations Hδ-⋅⋅⋅δ-H bonds are dominated by charge delocalization or London dispersion forces and the electrostatic term is also relevant. The side carbonyl ligands additionally stabilize the Hδ-⋅⋅⋅δ-H bonded structures through covalent charge delocalizations and Coulombic contributors. Furthermore, the sterically crowded systems containing bulky phosphine ligands are supported by π⋅⋅⋅π stacking, C-H⋅⋅⋅π and C-H⋅⋅⋅H-Co. It is finally determined by IQA energy decomposition, that diatomic hydride-hydride interaction CoH⋅⋅⋅HCo is chameleon-like, namely, it is attractive in CO4CoH⋅⋅⋅HCoCO4 and (PH3)4CoH⋅⋅⋅HCo(PH3)4, whereas the repulsion is unveiled in (CO)3(PPh3)CoH⋅⋅⋅HCo(CO)3(PPh3) where the monomers are of Cs symmetry.

Field-dependent abundances of hydride molecular ions in atom probe tomography of III-N semiconductors.

We investigate the microscopic behaviour of hydrogen-containing species formed on the surface of III-N semiconductor samples by the residual hydrogen in the analysis chamber in laser-assisted atom probe tomography (APT). We analysed AlGaN/GaN heterostructures containing alternate layers with a thickness of about 20 nm. The formation of H-containing species occurs at field strengths between 22 and 26 V/nm and is independent of the analysed samples. The 3D APT reconstruction makes it possible to map the evolution of the surface behaviour of these species issued by chemical reactions. The results highlight the strong dependence of the relative abundances of hydrides on the surface field during evaporation. The relative abundances of the hydrides decrease when the surface field increases due to the evolution of the tip shape or the different evaporation behaviour of the different layers.

Adsorption and storage of hydrogen- A computational model approach.

Due to the imperative global energy transition crisis, hydrogen storage and adsorption technologies are becoming popular with the growing hydrogen economy. Recently, complex hydrides have been one of the most reliable materials for storing and transporting hydrogen gas to various fuel cells to generate clean energy with zero carbon emissions. With the ever-increasing carbon emissions, it is necessary to substitute the current energy sources with green hydrogen-based efficient energy-integrated systems. Herein, we propose an input-output model that comprehends complex hydrides such as lithium and magnesium alanates, amides and borohydrides to predict, estimate, and directly analyse hydrogen storage and adsorption. A critical and thorough comparative analysis of the respective complex hydrides for hydrogen adsorption and storage is discussed, elucidating the storage applications in water bodies. Several industrial scale-up processes, economic analysis, and plant design of hydrogen storage and adsorption approaches are suggested through volumetric and gravimetric calculations.

Engineered Surface Chemistry and Enhanced Energetic Performance of Aluminum Nanoparticles by Nonthermal Hydrogen Plasma Treatment.

Extracting the maximum chemical energy from aluminum nanoparticles (Al NPs) during oxidation is essential for their use in energetic applications. However, the shell of native Al2O3 limits the release of chemical energy by acting as a diffusion barrier and dead weight. Engineering the surface properties of Al NPs by modifying their shell chemistry can reduce the inhibiting effects of the oxide shell on the rate and heat release of oxidation. Here, we employ nonthermal hydrogen plasma at high power and a short time to alter the shell chemistry by doping it with Al-H, as examined and confirmed by HRTEM, FTIR, and XPS. Thermal analysis (TGA/DSC) shows that Al NPs with modified surfaces exhibit augmented oxidation and heat release (33% higher than those of untreated Al NPs). The results demonstrate the promising effect of nonthermal hydrogen plasma in engineering the shell chemistry of Al NPs to improve their overall energetic performance during oxidation.

The Dimerization and Oligomerization of Alkenes Catalyzed with Transition Metal Complexes: Catalytic Systems and Reaction Mechanisms.

Dimers and oligomers of alkenes represent a category of compounds that are in great demand in diverse industrial sectors. Among the developing synthetic methods, the catalysis of alkene dimerization and oligomerization using transition metal salts and complexes is of undoubted interest for practical applications. This approach demonstrates substantial potential, offering not only elevated reaction rates but also precise control over the chemo-, regio-, and stereoselectivity of the reactions. In this review, we discuss the data on catalytic systems for alkene dimerization and oligomerization. Our focus lies in the analysis of how the activity and chemoselectivity of these catalytic systems are influenced by various factors, such as the nature of the transition metal, the ligand environment, the activator, and the substrate structure. Notably, this review particularly discusses reaction mechanisms, encompassing metal complex activation, structural and dynamic features, and the reactivity of hydride intermediates, which serve as potential catalytically active centers in alkene dimerization and oligomerization.

Unraveling Meso-Substituent Steric Effects on the Mechanism of Hydrogen Evolution Reaction in NiII Porphyrin Hydrides Using DFT Method.

Substituents at the meso-site of metalloporphyrins profoundly influence the hydrogen evolution reaction (HER) mechanism. This study employs density functional theory (DFT) to computationally analyze NiII-porphyrin and its hydrides derived from tetrakis(pentafluorophenyl)porphyrin molecules, presenting stereoisomers in ortho- or para-positions. The results reveal that the spatial resistance effect of meso-substituted groups at the ortho- and para-positions induces significant changes in Ni-N bond lengths, angles, and reaction dynamics. For ortho-position substituents forming complex I, a favorable 88.88 ų spherical space was created, facilitating proton coordination and the formation of H2 molecules; conversely, para-position substituents forming complex II impeded H2 formation until bimolecular complexes arose. Molecular dynamics (MD) analysis and comparison were conducted on the intermediation products of I-H2 and (II-H)2, focusing on the configuration and energy changes. In the I-H2 products, H2 molecules underwent separation after 150 fs and overcame the 2.2 eV energy barrier. Subsequently, significant alterations in the spatial structure were observed as complex I deformed. In the case of (II-H)2, it was influenced by the distinctive "sandwich" configuration; the spatial structure necessitated overcoming a 6.7 eV energy barrier for H2 detachment and a process observed after 2400 fs.

Metal-Free B-B Dehydrocoupling Reaction of a Simple Borane Adduct: Convenient Access to a Nucleophilic Diborane(4).

The selective formation of homonuclear bonds is of key importance in synthetic chemistry. Especially, dehydrocoupling reactions are attractive as ecologically and economically friendly alternatives to established reductive bond forming reactions, since they do not require the use of stoichiometric amounts of a reducing reagent and produce only valuable dihydrogen as by-product. Here, we report on a metal-free B-B dehydrocoupling reaction that starts directly from a simple, easily accessible BH3 adduct, providing convenient access to a new nucleophilic dihydridodiborane in excellent yield. The dihydridodiborane in turn activates dihydrogen, allowing to obtain quantitatively the dideuteridodiborane from the dihydridodiborane by D2 activation. On the basis of detailed quantum-chemical calculations, the mechanism of this unprecedented reaction is elucidated. Some key points that are essential for metal-free dehydrocoupling are disclosed, paving the way for their systematic evaluation and application.

Ba12 [BN2 ]6.67 H4 : A Disordered Anti-Skutterudite filled with Nitridoborate Anions.

Skutterudites are of high interest in current research due to their diversity of structures comprising empty, partially filled and filled variants, mostly based on metallic compounds. We herein present Ba12 [BN2 ]6.67 H4 , forming a non-metallic filled anti-skutterudite. It is accessed in a solid-state ampoule reaction from barium subnitride, boron nitride and barium hydride at 750 °C. Single-crystal X-ray and neutron powder diffraction data allowed to elucidate the structure in the cubic space group Im 3 ‾ ${\bar{3}}$ (no. 204). The barium and hydride atoms form a three-dimensional network consisting of corner-sharing HBa6 octahedra and Ba12 icosahedra. Slightly bent [BN2 ]3- units are located in the icosahedra and the voids in-between. 1 H and 11 B magic angle spinning (MAS) NMR experiments and vibrational spectroscopy further support the structure model. Quantum chemical calculations coincide well with experimental results and provide information about the electronic structure of Ba12 [BN2 ]6.67 H4 .

Why Mg2IrH6 Is Predicted to Be a High-Temperature Superconductor, But Ca2IrH6 Is Not.

The X2MH6 family, consisting of an electropositive cation X and a main group metal M octahedrally coordinated by hydrogen, has been predicted to hold promise for high-temperature conventional superconductivity. Herein, we analyze the electronic structure of two members of this family, Mg2IrH6 and Ca2IrH6, showing why the former may possess superconducting properties rivaling those of the cuprates, whereas the latter does not. Within Mg2IrH6 the vibrations of the IrH64- anions are key for the superconducting mechanism, and they induce coupling in the eg* set, which are antibonding between the H 1s and the Ir dx2-y2 or dz2 orbitals. Because calcium possesses low-lying d-orbitals, eg* → Ca d back-donation is preferred, quenching the superconductivity. Our analysis explains why high critical temperatures were only predicted for second or third row X metal atoms and may hold implications for superconductivity in other systems where the antibonding anionic states are filled.