Transition Metal Hydride Complexes Research Articles

Enhancing hydrogen positions in X-ray structures of transition metal hydride complexes with dynamic quantum crystallography.

Hirshfeld atom refinement (HAR) is a method which enables the user to obtain more accurate positions of hydrogen atoms bonded to light chemical elements using X-ray data. When data quality permits, this method can be extended to hydrogen-bonded transition metals (TMs), as in hydride complexes. However, addressing hydrogen thermal motions with HAR, particularly in TM hydrides, presents a challenge. At the same time, proper description of thermal vibrations can be vital for determining hydrogen positions correctly. In this study, we employ tools such as SHADE3 and Normal Mode Refinement (NoMoRe) to estimate anisotropic displacement parameters (ADPs) for hydrogen atoms during HAR and IAM refinements performed for seven structures of TM (Fe, Ni, Cr, Nb, Rh and Os) and metalloid (Sb) hydride complexes for which both the neutron and the X-ray structures have been determined. A direct comparison between neutron and HAR/SHADE3/NoMoRe ADPs reveals that the similarity between neutron hydrogen ADPs and those estimated with NoMoRe or SHADE3 is significantly higher than when hydrogen ADPs are refined with HAR. Regarding TM-H bond lengths, traditional HAR exhibits a slight advantage over the other methods. However, combining NoMoRe/SHADE3 with HAR results in a minor decrease in agreement with neutron TM-H bond lengths. For the Cr complex, for which high-resolution X-ray data were collected, an investigation of resolution-related effects was possible.

The Notable Catalytic Activity of Transition Metal Thiolate Complexes against Hydrosilylation and Hydroboration of Carbon-Heteroatom Bonds.

Chemists tend to use transition metal hydride complexes rather than thiolate complexes to catalyse chemical transformations because the hydride complexes possess diverse catalytic reactivity although most of them are air/moisture sensitive and difficult to prepare. By comparing the catalytic performances of pincer ligated group 10 metal thiolate and hydride complexes in catalysing the hydroboration and hydrosilylation of C=O and C=N bonds, we demonstrate in this review that transition metal thiolate complexes are much better catalysts than the corresponding hydride complexes in catalysing this type of reactions. Many hydroboration and hydrosilylation reactions catalysed by pincer ligated group 10 metal hydride complexes can also be catalysed by the corresponding thiolate complexes and the thiolate systems are far more active. Therefore, the applications of transition metal thiolate complexes in the catalytic hydroboration and hydrosilylation of unsaturated carbon-heteroatom bonds deserve special attention in future work.

Proton transfer kinetics of transition metal hydride complexes and implications for fuel-forming reactions.

Proton transfer reactions involving transition metal hydride complexes are prevalent in a number of catalytic fuel-forming reactions, where the proton transfer kinetics to or from the metal center can have significant impacts on the efficiency, selectivity, and stability associated with the catalytic cycle. This review correlates the often slow proton transfer rate constants of transition metal hydride complexes to their electronic and structural descriptors and provides perspective on how to exploit these parameters to control proton transfer kinetics to and from the metal center. A toolbox of techniques for experimental determination of proton transfer rate constants is discussed, and case studies where proton transfer rate constant determination informs fuel-forming reactions are highlighted. Opportunities for extending proton transfer kinetic measurements to additional systems are presented, and the importance of synergizing the thermodynamics and kinetics of proton transfer involving transition metal hydride complexes is emphasized.

Rotation of complex ions with ninefold hydrogen coordination studied by quasielastic neutron scattering and first-principles molecular dynamics calculations

Quasielastic neutron scattering (QENS) and neutron powder diffraction of the complex transition metal hydrides ${\mathrm{Li}}_{5}{\mathrm{MoH}}_{11}$ and ${\mathrm{Li}}_{6}{\mathrm{NbH}}_{11}$ were measured in a temperature range of 10--300 K to study their structures and dynamics, especially the dynamics of the hydrogen atoms. These hydrides contain unusual ninefold H-coordinated complex ions (${\mathrm{MoH}}_{9}^{3\ensuremath{-}}$ or ${\mathrm{NbH}}_{9}^{4\ensuremath{-}}$) and hydride ions $({\mathrm{H}}^{\ensuremath{-}})$. A QENS signal appeared >150 K due to the relaxation of H atoms. The intermediate scattering functions derived from the QENS spectra are well fitted by a stretched exponential function called the Kohlrausch-Williams-Watts functions with a small stretching exponent \ensuremath{\beta} \ensuremath{\approx} 0.3--0.4, suggesting a wide relaxation time distribution. The $Q$ dependence of the elastic incoherent structure factor is reproduced by the rotational diffusion of $M{\mathrm{H}}_{9}$ ($M=\mathrm{Mo}$ or Nb) anions. The results are well supported by a van Hove analysis for the motion of H atoms obtained using first-principles molecular dynamics calculations. We conclude that the wide relaxation time distribution of the $M{\mathrm{H}}_{9}$ rotation is due to the positional disorder of the surrounding Li ions and a unique rotation with $M{\mathrm{H}}_{9}$ anion deformation (pseudorotation).

Thermochemical Studies of Nickel Hydride Complexes with Cationic Ligands in Aqueous and Organic Solvents

Transition metal hydride complexes are key intermediates in a variety of catalytic processes. Transfer of a hydride, hydrogen atom, or proton is defined by the thermochemical parameters of hydricity, bond dissociation free energy (BDFE), and pKa, respectively. These values have been studied primarily in organic solvents to predict or understand reactivity. Despite growing interest in the development of aqueous metal hydride catalysis, BDFE measurements of transition metal hydrides in water are rare. Herein, we report two nickel hydride complexes with one or two cationic ligands that enable the measurement of BDFE values in both aqueous and organic solvents using their reduction potential and pKa values. The Ni(I/0) reduction potentials increase anodically as more charged groups are introduced into the ligand framework and are among the most positive values measured for Ni complexes. The complex with two cationic ligands, 2-Ni(II)–H, displays exceptional stability in water with no evidence of decomposition at pH 1 for at least 2 weeks. The BDFE of the nickel hydride bond in 2-Ni(II)–H was measured to be 53.6 kcal/mol in water and between 50.9 and 56.2 kcal/mol in acetonitrile, consistent with prior work that indicates minimal solvent dependence for BDFEs of O–H and N–H bonds. These results indicate that transition metal hydride BDFEs do not change drastically in water and inform future studies on highly cationic transition metal hydride complexes.

Insights into the Capture of CO2 by Nickel Hydride Complexes

As a desired feedstock for sustainable energy source and for chemical synthesis, the capture and utilization of CO2 have attracted chemists’ continuous efforts. The homogeneous CO2 insertion into a nickel hydride complex to generate formate provides insight into the role of hydrogen as an active hydride form in the hydrogenation of CO2, which serves as a practicable approach for CO2 utilization. To parameterize the activities and to model the structure–activity relationship in the CO2 insertion into nickel hydride, the comprehensive mechanism of CO2 insertion into a series of square planar transition metal hydride (TM–H, TM = Ni, Pd, and Co) complexes was investigated using density functional theory (DFT) computations. The stepwise pathway with the TM-(H)-formate intermediate for the CO2 insertion into all seven square planar transition metal hydride (TM–H) complexes was observed. The overall rate-determining step (RDS) was the nucleophilic attraction of the terminal O atom on the Ni center in Ni-(H)-formate to form Ni-(O)-(exo)formate. The charge of the Ni atom in the axially vacant [Ni]+ complex was demonstrated as the dominant factor in CO2 insertion, which had an excellent linear correction (R2 = 0.967) with the Gibbs barrier (ΔG‡) of the RDS. The parameterized activities and modeled structure–activity relationship provided here light the way to the design of a more efficient Ni–H complex in the capture and utilization of CO2.

Influence of phosphine (pincer) ligands on the transition metal hydrides reactivity

• Dihydrogen bonding determines reactivity of metal hydrides. • Role of (di)hydrogen bonding and proton transfer in (de)hydrogenation processes. • Steric and electronic effects of phosphines on the reactivity. • Reactivity of palladium, nickel, iridium and rutenium pincer hydrides. Transition-metal hydride complexes are plenteous in organometallic chemistry. The reactivity of metal hydrides is determined by three possible pathways of M–H bond cleavage: homolytic cleavage yielding a hydrogen radical (H ), and heterolytic cleavage generating either a proton (H + ) or hydride (H − ). These steps, especially the proton and hydride transfer, are critical in a vast array of stoichiometric and catalytic transformations. Many late transition metal hydrides are supported by phosphine ligands, which allow tuning the electronic and steric properties at a metal center in a systematic and predictable way. In this non-exhaustive review we attempt to trace the influence of phosphines properties on the reactivity of transition metal hydrides in topical stoichiometric and catalytic processes highlighting the reactions’ mechanisms and the role of hydrogen bonding interactions in the intermediates of hydrogen transfer reactions.

Towards accurate and precise positions of hydrogen atoms bonded to heavy metal atoms.

A comparison of five X-ray structures of transition-metal-bound hydride complexes, successfully refined using Hirshfeld Atom Refinement (HAR) against low resolution X-ray diffraction data (including the positions and ADPs of all hydrogen atoms), with neutron structures shows that using aspherical atomic scattering factors instead of spherical ones results in systematic elongation of metal-hydrogen bonds, which in the case of the highest-quality data leads to excellent agreement of the X-ray and the neutron-derived bond lengths.

Accurate and rapid prediction of pKa of transition metal complexes: semiempirical quantum chemistry with a data-augmented approach.

Rapid and accurate prediction of reactivity descriptors of transition metal (TM) complexes is a major challenge for contemporary quantum chemistry. The recently-developed GFN2-xTB method based on the density functional tight-binding theory (DFT-B) is suitable for high-throughput calculation of geometries and thermochemistry for TM complexes albeit with moderate accuracy. Herein we present a data-augmented approach to improve substantially the accuracy of the GFN2-xTB method for the prediction of thermochemical properties using pKa values of TM hydrides as a representative model example. We constructed a comprehensive database for ca. 200 TM hydride complexes featuring the experimentally measured pKa values as well as the GFN2-xTB-optimized geometries and various computed electronic and energetic descriptors. The GFN2-xTB results were further refined and validated by DFT calculations with the hybrid PBE0 functional. Our results show that although the GFN2-xTB performs well in most cases, it fails to adequately describe TM complexes featuring multicarbonyl and multihydride ligand environments. The dataset was analyzed with the ordinary least squares (OLS) fitting and was used to construct an automated machine learning (AutoML) approach for the rapid estimation of pKa of TM hydride complexes. The results obtained show a high predictive power of the very fast AutoML model (RMSE ∼ 2.7) comparable to that of the much slower DFT calculations (RMSE ∼ 3). The presented data-augmented quantum chemistry-based approach is promising for high-throughput computational screening workflows of homogeneous TM-based catalysts.

Metalloradical complex Co-C˙Ph3 catalyzes the CO2 reduction in gas phase: a theoretical study.

Metal-stabilized radicals have been increasingly exploited in modern organic synthesis. Here, we theoretically designed a metalloradical complex Co-C˙Ph3 with the triplet characters through the transition metal cobalt (Co0) coordinating a triphenylmethyl radical. The potential catalytic role of this novel metalloradical in the CO2 reduction with H2/CH4 in the gas phase was explored via density functional theory (DFT) calculations. For the CO2 reduction reaction with H2, there are two possible pathways: one (path A) is the activation of CO2 by Co-C˙Ph3, followed by the hydrogenation of CO2. The other (path B) starts from the splitting of the H-H bond by Co-C˙Ph3, leading to the transition-metal hydride complex CoH-H, which can reduce CO2. DFT computations show that path B is more favorable than path A as their rate-determining free energy barriers are 18.3 and 27.2 kcal mol-1, respectively. However, for the reduction of CO2 by CH4 two different products, CH3COOH and HCOOCH3, can be generated following different reaction routes. Both routes begin with one CH4 molecule approaching the metalloradical Co-C˙Ph3 to form the intermediate CoH-CH3. This intermediate can evolve following two different pathways, depending on whether the H bonded to Co is transferred to the O (pathway PO) or the C (pathway PC) of CO2. Comparing their rate-determining steps, we identified that the PO route is more favorable for the reduction of CO2 by CH4 to CH3COOH with the reaction barrier 24.5 kcal mol-1. Thus, the present Co0-based metalloradical system represents a viable catalytic protocol that can contribute to the effective utilization of small molecules (H2 and CH4) to reduce CO2, and provides an alternative strategy for the exploration of CO2 conversion.

First-Principles Calculation of 1H NMR Chemical Shifts of Complex Metal Polyhydrides: The Essential Inclusion of Relativity and Dynamics.

1H NMR spectroscopy has become an important technique for the characterization of transition-metal hydride complexes, whose metal-bound hydrides are often difficult to locate by X-ray diffraction. In this regard, the accurate prediction of 1H NMR chemical shifts provides a useful, but challenging, strategy to help in the interpretation of the experimental spectra. In this work, we establish a density-functional-theory protocol that includes relativistic, solvent, and dynamic effects at a high level of theory, allowing us to report an accurate and reliable interpretation of 1H NMR hydride chemical shifts of iridium polyhydride complexes. In particular, we have studied in detail the hydride chemical shifts of the [Ir6(IMe)8(CO)2H14]2+ complex in order to validate previous assignments. The computed 1H NMR chemical shifts are strongly dependent on the relativistic treatment, the choice of the DFT exchange–correlation functional, and the conformational dynamics. By combining a fully relativistic four-component electronic-structure treatment with ab initio molecular dynamics, we were able to reliably model both the terminal and bridging hydride chemical shifts and to show that two NMR hydride signals were inversely assigned in the experiment.

Systematic Trends in the Electrochemical Properties of Transition Metal Hydride Complexes Discovered by Using the Ligand Acidity Constant Equation.

Understanding the thermodynamics of paramagnetic transition metal hydride complexes, especially of the abundant 3d metals, is important in the design of electrocatalysts and organometallic catalysts. The pKaMeCN([MHLn]+/[MLn) of paramagnetic hydrides in MeCN are estimated for the first time using the ligand acidity constant (LAC) equation where contributions to the pKaMeCN from each ligand are simply added together, with the sum corrected for effects of charge and 5d metals. The pKaLAC-MeCN([MHLn]+/MLn) of over 200 hydride complexes MHLn are used, along with their electrochemical potentials from the literature, in an uncommonly applied thermochemical cycle in order to reveal systematic trends in the redox couples MIII/II and MV/IV (M = Cr, Mo, W), MnII/I, ReVI/V and ReIV/III, MIII/II and MIV/III (M = Fe, Ru, Os), and MIII/II and MII/I (M = Co, Rh, and Ir) and allow the estimation of the bond dissociation free energies BDFE(MH) of the unoxidized hydrides MHLn and the prediction of the electrochemical potential for their oxidation. Density functional theory (DFT) calculations are used to validate the pKaLAC-MeCN values of hydrides of WIII, MnII, FeIII, RuIII, CoII, and NiIII. When a pKaLAC-MeCN is less than zero for a given complex [MHLn]+, the oxidation of MHLn is irreversible due to proton loss from the oxidized complex to the solvent. When pKaLAC-MeCN ≫ 0, the oxidation is reversible when there is no gross change in the coordination geometry upon a change in the redox state. Twenty paramagnetic hydrides prepared in bulk all have pKaLAC-MeCN > 8.

Pseudorotating hydride complexes with high hydrogen coordination: A class of rotatable polyanions in solid matter

Solid-state materials containing rotatable polyanions, such as B12H122−, constitute a peculiar class of ionic conductors due to their unique transport behavior, where rotating polyanions promote phase transitions to disordered phases with several orders of magnitude enhancement in cation conductivities. A major drawback is the high temperature required to activate rotation and thereby low conductivities at room temperature. Here, we elucidate a mechanism to drastically reduce the temperature based on the use of pseudorotation in high-H coordination hydride complexes. We demonstrate this mechanism for an existing complex transition metal hydride Li5MoH11 containing MoH93−, and we present a strong potential of this material to unprecedentedly exhibit a high lithium ion conductivity of 7.9 × 10–2 S cm−1 at room temperature.

Synthesis and Diverse Transformations of a Dinitrogen Dititanium Hydride Complex Bearing Rigid Acridane-Based PNP-Pincer Ligands.

Studies on N2 activation and transformation by transition metal hydride complexes are of particular interest and importance. The synthesis and diverse transformations of a dinitrogen dititanium hydride complex bearing the rigid acridane-based acri PNP-pincer ligands {[(acri PNP)Ti]2 (μ2 -η1 :η2 -N2 )(μ2 -H)2 } are presented. This complex enabled N2 cleavage and hydrogenation even without additional H2 or other reducing agents. Furthermore, diverse transformations of the N2 unit with a variety of organometallic compounds such as ZnMe2 , MgMe2 , AlMe3 , B(C6 F5 )3 , PinBH, and PhSiH3 have been well established at the rigid acri PNP-ligated dititanium framework, such as reversible bonding-mode change between the end-on and side-on/end-on fashions, diborylative N=N bond cleavage, the formal insertion of two dimethylaluminum species into the N=N bond, and the formal insertion of two silylene units into the N=N bond. This work has revealed many unprecedented aspects of dinitrogen reaction chemistry.

Synthesis and Diverse Transformations of a Dinitrogen Dititanium Hydride Complex Bearing Rigid Acridane‐Based PNP‐Pincer Ligands

AbstractStudies on N2 activation and transformation by transition metal hydride complexes are of particular interest and importance. The synthesis and diverse transformations of a dinitrogen dititanium hydride complex bearing the rigid acridane‐based acriPNP‐pincer ligands {[(acriPNP)Ti]2(μ2‐η1:η2‐N2)(μ2‐H)2} are presented. This complex enabled N2 cleavage and hydrogenation even without additional H2 or other reducing agents. Furthermore, diverse transformations of the N2 unit with a variety of organometallic compounds such as ZnMe2, MgMe2, AlMe3, B(C6F5)3, PinBH, and PhSiH3 have been well established at the rigid acriPNP‐ligated dititanium framework, such as reversible bonding‐mode change between the end‐on and side‐on/end‐on fashions, diborylative N=N bond cleavage, the formal insertion of two dimethylaluminum species into the N=N bond, and the formal insertion of two silylene units into the N=N bond. This work has revealed many unprecedented aspects of dinitrogen reaction chemistry.

Proton-Coupled Electron Transfer Kinetics for the Photoinduced Generation of a Cobalt(III)-Hydride Complex.

Studying the formation of transition metal hydride complexes via proton-coupled electron transfer is important for developing next-generation molecular catalysts for hydrogen evolution. We report herein the study of stepwise photoinduced reduction and protonation of [CoIICp(dppe)]+ (Cp = cyclopentadienyl, dppe = 1,2-bis(diphenylphosphino)ethane) to form the corresponding hydride complex [HCoIIICp(dppe)]+. Reaction intermediates were optically tracked using transient absorption spectroscopy, and a combination of experimental fitting and kinetic simulations was used to determine apparent rate constants for electron transfer and proton transfer with a range of acid sources. A linear free energy relationship is observed between measured apparent proton transfer rate constants and acid strength, but marked differences from previously electrochemically determined protonation rate constants are found. These deviations, which stem from ground-state reactivity present in photochemical experiments, highlight the challenges in comparing mechanistic studies using different techniques.

Exploring the Mg-Cr-H System at High Pressure and Temperature via in Situ Synchrotron Diffraction.

The complex transition metal hydride Mg3CrH8 has been previously synthesized using high pressure conditions. It contains the first group 6 homoleptic hydrido complex, [Cr(II)H7]5-. Here, we investigated the formation of Mg3CrH8 by in situ studies of reaction mixtures of 3MgH2-Cr-H2 at 5 GPa. The formation of the known orthorhombic form (o-Mg3CrH8) was noticed at temperatures above 635 °C, albeit at a relatively slow rate. At temperatures around 750 °C a high temperature phase formed rapidly, which upon slow cooling converted into o-Mg3CrH8. The phase transition at high pressures occurred reversibly at ∼735 °C upon heating and at ∼675 °C upon slow cooling. Upon rapid cooling, a monoclinic polymorph (m-Mg3CrH8) was afforded which could be subsequently recovered and analyzed at ambient pressure. m-Mg3CrH8 was found to crystallize in P21/n space group (a = 5.128 Å, b = 16.482 Å, c = 4.805 Å, β = 90.27°). Its structure elucidation from high resolution synchrotron powder diffraction data was aided by first-principles DFT calculations. Like the orthorhombic polymorph, m-Mg3CrH8 contains pentagonal bipyramidal complexes [CrH7]5- and interstitial H-. The arrangement of metal atoms and interstitial H- resembles closely that of the high pressure orthorhombic form of Mg3MnH7. This suggests similar principles of formation and stabilization of hydrido complexes at high pressure and temperature conditions in the Mg-Cr-H and Mg-Mn-H systems. Calculated enthalpy versus pressure relations predict o-Mg3CrH8 being more stable than m-Mg3CrH8 by 6.5 kJ/mol at ambient pressure and by 13 kJ/mol at 5 GPa. The electronic structure of m-Mg3CrH8 is very similar to that of o-Mg3CrH8. The stable 18-electron complex [CrH7]5- is mirrored in the occupied states, and calculated band gaps are around 1.5 eV.

Catalytic recycling of NAD(P)H

A large number of industrially relevant enzymes depend upon dihydronicotinamide adenine dinucleotide (NADH) and dihydronicotinamide adenine dinucleotide phosphate (NADPH) cofactors, which are too expensive to be added in stoichiometric amounts. Existing NAD(P)H-recycling systems suffer from low activity, or the generation of side products. This review focuses on NAD(P)H cofactor regeneration catalyzed by transition metal complexes such as rhodium, ruthenium and iridium complexes using cheap reducing agents such as hydrogen (H2) and ethanol, which have attracted increasing attention as sustainable energy carriers. The catalytic mechanisms for the regioselective reduction of NAD(P)+ are discussed with emphasis on identification of catalytically active intermediates such as transition metal hydride complexes. Applications of NAD(P)H-recycling systems to develop artificial photosynthesis are also discussed.

Thermodynamic Hydricity of [FeFe]-Hydrogenases.

After remaining elusive for many years, terminal hydride states have now been identified in several native and mutant [FeFe]-hydrogenases. In this Perspective, hydride states of [FeFe]-hydrogenases are considered on the basis of hydricity, a thermodynamic parameter that has been instrumental for the rational design of synthetic molecular catalysts. Importantly, it is shown how the hydricity of [FeFe]-hydrogenases can inspire future research efforts in both the study of hydrogenases and the design of molecular catalysts. By using hydricity, quantitative linear free energy relationships can be developed to relate the driving force and rate of different [FeFe]-hydrogenase variants. Further development of these correlations across a wide range of hydrogenase variants can potentially lead to new insights into the structure-activity relationships of [FeFe]-hydrogenases. The hydricity of [FeFe]-hydrogenase is also compared to select transition metal hydride complexes, which emphasizes the strong electronic communication between the diiron active site and the extended protein scaffold of the enzyme. A mechanism is proposed for how key hydrogen bonding interactions might affect the hydricity of [FeFe]-hydrogenases, providing a basis for the emulation of these structural features in synthetic molecular complexes.

Hydrogen-Release Reaction of a Complex Transition Metal Hydride with Covalently Bound Hydrogen and Hydride Ions.

The hydrogen-release reaction of a complex transition metal hydride, LaMg2 NiH7 , composed of La3+ , 2×Mg2+ , [NiH4 ]4- and 3×H- , was studied by thermal analyses, powder X-ray, and neutron diffraction and inelastic neutron scattering. Upon heating, LaMg2 NiH7 released hydrogen at approximately 567 K and decomposed into LaH2-3 and Mg2 Ni. Before the reaction, covalently bound hydrogen (Hc °v. ) in [NiH4 ]4- exhibited a larger atomic displacement than H- , although a weakening of the chemical bonds around [NiH4 ]4- and H- was observed. These results indicate the precursor phenomenon of a hydrogen-release reaction, wherein there is a large atomic displacement of Hc °v. that induces the hydrogen-release reaction rather than H- . As an isothermal reaction, LaMg2 NiH7 formed LaMg2 NiH2.4 at 503 K in vacuum for 48 h, and LaMg2 NiH2.4 reacted with hydrogen to reform LaMg2 NiH7 at 473 K under 1 MPa of H2 gas pressure for 10 h. These results revealed that LaMg2 NiH7 exhibited partially reversible hydrogen-release and uptake reactions.