D-block Transition Metals Research Articles

Density Functional Tight-Binding Models for Band Structures of Transition-Metal Alloys and Surfaces across the d-Block.

First-principles electronic structure simulations are an invaluable tool for understanding chemical bonding and reactions. While machine-learning models such as interatomic potentials significantly accelerate the exploration of potential energy surfaces, electronic structure information is generally lost. Particularly in the field of heterogeneous catalysis, simulated electron band structures provide fundamental insights into catalytic reactivity. This ab initio knowledge is preserved in semiempirical methods such as density functional tight binding (DFTB), which extend the accessible computational length and time scales beyond first-principles approaches. In this paper we present Shell-Optimized Atomic Confinement (SOAC) DFTB electronic-part-only parametrizations for bulk and surface band structures of all d-block transition metals that enable efficient predictions of electronic descriptors for large structures or high-throughput studies on complex systems outside the computational reach of density functional theory.

Oxidative Addition of E-H (E=C, N) Bonds to Transient Uranium(II) Centers.

Two-electron oxidative addition is one of the most important elementary reactions for d-block transition metals but it is uncommon for f-block elements. Here, we report the first examples of intermolecular oxidative addition of E-H (E=C, N) bonds to uranium(II) centers. The transient U(II) species was formed in-situ by reducing a heterometallic cluster featuring U(IV)-Pd(0) bonds with potassium-graphite (KC8). Oxidative addition of C-H or N-H bonds to the U(II) centers was observed when this transient U(II) species was treated with benzene, carbazole or 1-adamantylamine, respectively. The U(II) centers could also react with tetracene, biphenylene or N2O, leading to the formation of arene reduced U(IV) products and uranyl(VI) species via two- or four-electron processes. This study demonstrates that the intermolecular two-electron oxidative addition reactions are viable for actinide elements.

Electronic Delocalization and σ-Aromaticity in Heterometallic Cluster with Multiple Thorium-Palladium Bonds.

Research on metal-metal bonds involving f-block actinides, such as thorium, lags far behind the well-studied metal-metal bonds of d-block transition metals. The complexes with Th-TM bonds are extremely rare; all previously identified examples have only a single Th-TM bond with the Th center at an invariably +IV oxidation state. Herein, we report a series of Th2Pdn (n = 2, 3, and 6) clusters (complexes 3, 4, and 7) with multiple Th(III)-Pd bonds. Theoretical studies reveal that the Th2Pdn unit allows electronic delocalization and σ aromaticity, leading to unexpected closed-shell singlet structures for these Th(III) species. This electronic delocalization is evident in the highest occupied molecular orbital of Th(III) complexes and facilitates a 2e reduction of alkyne by complex 7, resulting in the formation of 8. Complexes 7 and 8 are distinctive in featuring a Th2Pd6 core with six and eight Th-Pd bonds, respectively, making them the largest known d-f heterometallic clusters exhibiting metal-metal bonding.

Synergistic Electronic Interaction of Nitrogen Coordinated Fe-Sn Double-Atom Sites: An Efficient Electrocatalyst for Oxygen Reduction Reaction.

Double-atom site catalysts (DASs) have emerged as a recent trend in the oxygen reduction reaction (ORR), thereby modifying the intermediate adsorption energies and increasing the activity. However, the lack of an efficient dual atom site to improve activity and durability has limited these catalysts from widespread application. Herein, the nitrogen-coordinated iron and tin-based DASs (Fe-Sn-N/C) catalyst are synthesized for ORR. This catalyst has a high activity with ORR half-wave potentials (E1/2) of 0.92V in alkaline, which is higher than those of the state-of-the-art Pt/C (E1/2=0.83V), Fe-N/C (E1/2=0.83V), and Sn-N/C (E1/2=0.77V). Scanning electron transmission microscopy analysis confirmed the atomically distributed Fe and Sn sites on the N-doped carbon network. X-ray absorption spectroscopy analysis revealed the charge transfer between Fe and Sn. Both experimental and theoretical results indicate that the Sn with Fe-NC (Fe-Sn-N/C) induces charge redistribution, weakening the binding strength of oxygenated intermediates and leading to improved ORR activity. This study provides the synergistic effects of DASs catalysts and addresses the impacts of P-block elements on d-block transition metals in ORR.

Enriching 2D transition metal borides via MB XMenes (M = Fe, Co, Ir): Strong correlation and magnetism.

Recently, two-dimensional (2D) FeSe-like anti-MXenes (or XMenes), composed of late d-block transition metal M and p-block nonmetal X elements, have been both experimentally and theoretically investigated. Here, we select three 2D borides FeB, CoB and IrB for a deeper investigation by including strong correlation effects, as a fertile ground for understanding and applications. Using a combination of Hubbard corrected first-principles calculations and Monte Carlo simulations, FeB and CoB are found to be ferro- and anti-ferro magnetic, contrasting with the non-magnetic nature of IrB. The metallic FeB XMene monolayer, superior to most of the MXenes or MBenes, exhibits robust ferromagnetism, driven by intertwined direct-exchange and super-exchange interactions between adjacent Fe atoms. The predicted Curie temperature (TC) of the FeB monolayer via the Heisenberg model reaches an impressive 425 K, with the easy-axis oriented out-of-plane and high magnetic anisotropic energy (MAE). The asymmetry in the spin-resolved transmission spectrum induces a thermal spin current, providing an opportunity for spin filtration. This novel 2D FeB material is expected to hold great promise as an information storage medium and find applications in emerging spintronic devices.

Participation of transition metal atoms in noncovalent bonds.

The existence of halogen, chalcogen, pnicogen, and tetrel bonds as variants of noncovalent σ and π-hole bonds is now widely accepted, and many of their properties have been elucidated. The ability of the d-block transition metals to potentially act as Lewis acids in a similar capacity is examined systematically by DFT calculations. Metals examined span the entire range of the d-block from Group 3 to 12, and are selected from several rows of the periodic table. These atoms are placed in a variety of neutral MXn molecules, with X = Cl and O, and paired with a NH3 nucleophile. The resulting M⋯N bonds tend to be stronger than their p-block analogues, many of them with a substantial degree of covalency. The way in which the properties of these bonds is affected by the row and column of the periodic table from which the M atom is drawn, and the number and nature of ligands, is elucidated.

Single-atom catalysis in space: Computational exploration of Fischer–Tropsch reactions in astrophysical environments

Context. Gas-phase chemistry at extreme conditions (low densities and temperatures) is difficult, so the presence of interstellar grains is especially important for the synthesis of molecules that cannot form in the gas phase. Interstellar grains are advocated to enhance the encounter rate of the reactive species on their surfaces and to dissipate the energy excess of largely exothermic reactions, but less is known of their role as chemical catalysts that provide low activation energy pathways with enhanced reaction rates. Different materials with catalytic properties are present in interstellar environments, like refractory grains containing space-abundant d-block transition metals. Aims. In this work we report for first time mechanistic insights on the Fischer–Tropsch methanol (CH3OH) synthesis under astrophysical conditions using single-atom Fe-containing silica surfaces as interstellar heterogeneous catalysts. Methods. Quantum chemical calculations considering extended periodic surfaces were carried out in order to search for the stationary points and transitions states to finally construct the reaction potential energy surfaces. Binding energy and kinetic calculations based on the Rice–Ramsperger–Kassel–Marcus (RRKM) scheme were also performed to evaluate the catalytical capacity of the grain and to allocate those reaction processes within the astrochemical framework. Results. Our mechanistic studies demonstrate that astrocatalysis is feasible in astrophysical environments. Thermodynamically the proposed process is largely exergonic, but kinetically it shows energy barriers that would need from an energy input in order to go through. Kinetic calculations also demonstrate the strong temperature dependency of the reaction process as tunnelling is not relevant in the involved energetic barriers. The present results can explain the presence of CH3OH in diverse regions where current models fail to reproduce its observational quantity. Conclusions. The evidence of astrocatalysis opens a completely new spectrum of synthetic routes triggering chemical evolution in space. From the mechanistic point of view the formation of methanol catalysed by a single atom of Fe0 is feasible; however, its dependency on the temperature makes the energetics a key issue in this scenario.

Regulating the generation of reactive oxygen species for photocatalytic oxidation by metalloporphyrinic covalent organic frameworks

Regulating the generation of reactive oxygen species (ROS) impacts the selectivity and activity of photocatalytic oxidation, but the frequently concurrent formation of different types of ROS makes this process rather challenging. This study demonstrates the regulated production of two important ROS, 1O2 and O2•−, using a covalent-organic framework (COF) array with three members, which are made up of metalloporphyrin cores with embedded center metal ions from d-block transition metals sequentially arranged in the periodic table. Due to the evolution of the electronic structures in this COF array, the production of 1O2 and O2•− is controlled, which successively leads to distinct performance in photocatalytic aerobic oxidations. The electronic property study and density-functional theory (DFT) calculations revealed that the distinct excitonic behavior of three COFs in regulated 1O2 and O2•− generation is rooted in their different band energy levels and O2 adsorption ability. Our work presents an effective approach to the controlled production of ROS for improved photocatalytic performance.

Heterometallic Clusters with Cerium-Transition-Metal Bonding Supported by Nitrogen-Phosphorus Ligands.

Ligands are known to play a crucial role in the construction of complexes with metal-metal bonds. Compared with metal-metal bonds involving d-block transition metals, knowledge of the metal-metal bonds involving f-block rare-earth metals still lags far behind. Herein, we report a series of complexes with cerium-transition-metal bonds, which are supported by two kinds of nitrogen-phosphorus ligands N[CH2CH2NHPiPr2]3 (VI) and PyNHCH2PPh2 (VII). The reactions of zerovalent group 10 metal precursors, Pd(PPh3)4 and Pt(PPh3)4, with the cerium complex supported by VI generate heterometallic clusters [N{CH2CH2NPiPr2}3Ce(μ-M)]2 (M = Pd, 2 and M = Pt, 3) featuring four Ce-M bonds; meanwhile, the bimetallic species [(PyNCH2PPh2)3Ce-M] (M = Ni, 5; M = Pd, 6; and M = Pt, 7) with a single Ce-M bond were isolated from the reactions of the cerium precursor 4 supported by VII with Ni(COD)2, Pd(PPh3)4, or Pt(PPh3)4, respectively. These complexes represent the first example of species with an RE-M bond between Ce and group 10 metals, and 2 and 3 contain the largest number of RE-M donor/acceptor interactions ever to have been observed in a molecule.

Synthesis and characterization of a formal 21-electron cobaltocene derivative

Metallocenes are highly versatile organometallic compounds. The versatility of the metallocenes stems from their ability to stabilize a wide range of formal electron counts. To date, d-block metallocenes with an electron count of up to 20 have been synthesized and utilized in catalysis, sensing, and other fields. However, d-block metallocenes with more than formal 20-electron counts have remained elusive. The synthesis and isolation of such complexes are challenging because the metal–carbon bonds in d-block metallocenes become weaker with increasing deviation from the stable 18-electron configuration. Here, we report the synthesis, isolation, and characterization of a 21-electron cobaltocene derivative. This discovery is based on the ligand design that allows the coordination of an electron pair donor to a 19-electron cobaltocene derivative while maintaining the cobalt–carbon bonds, a previously unexplored synthetic approach. Furthermore, we elucidate the origin of the stability, redox chemistry, and spin state of the 21-electron complex. This study reveals a synthetic method, structure, chemical bonding, and properties of the 21-electron metallocene derivative that expands our conceptual understanding of d-block metallocene chemistry. We expect that this report will open up previously unexplored synthetic possibilities in d-block transition metal chemistry, including the fields of catalysis and materials chemistry.

Heterotrimetallic clusters with U-Ni-Ge and U-Ni-Sn units

Metal-metal bonds in complexes with d-block transition metals are common; but those with metal–metal bonds involving both p-, d-, and f-block metals are extremely rare. Here, we report two examples of heterotrimetallic clusters featuring U-Ni-Ge and U-Ni-Sn units. The heterotrimetallic clusters [(CH2OCH2CH2NPiPr2)2U(µ-Ni)(GePh3)(µ-Cl)]2 (2) and [(CH2OCH2CH2NPiPr2)2U(µ-Ni)(SnPh3)(µ-Cl)]2 (3) were synthesized by the salt elimination reactions of [(CH2OCH2CH2NPiPr2)2UCl(µ-Ni)(µ-Cl)]n (1) with Ph3SnK or Ph3GeLi, respectively. Complexes 2 and 3 were fully characterized by single crystal X-ray diffraction, elemental analysis, UV–Vis-NIR and SQUID. Theoretical studies at the DFT level showed that the Ni-Ge and Ni-Sn bonding interactions are polarized toward Ge and Sn. In both cases, the covalent part of the bonding is controlled by the atomic orbital overlap rather than by the energy difference. This study provides a new opportunity to explore the property of heterometallic clusters with diversified metal–metal bonds.

P-Block-metal bismuth-based electrocatalysts featuring tunable selectivity for high-performance oxygen reduction reaction

•The discovery of p-block-metal bismuth-based ORR electrocatalysts is reported •The metallic Bi nanoparticles exhibit outstanding activity for H2O2 production •The single-atomic-site Bi catalysts give excellent performance for 4e− ORR •DFT calculations explain the origin of the high performance of Bi-based ORR catalysts For oxygen reduction reaction (ORR), replacing the conventional electrocatalysts based on platinum-group metals (PGMs) with alternatives based on non-noble metals is vital for the large-scale applications of green energy conversion and chemical synthesis. Here, we report the discovery of ORR catalysts based on the p-block-metal bismuth (Bi); the selectivity in ORR pathways could be controlled by tailoring the size of Bi. Specifically, the metallic Bi nanoparticles gave a high selectivity (>96%) for 2e− ORR, an ultra-high kinetic current density (3.8 mA·cm−2 at 0.65 V), and an excellent stability; in contrast, the single-atomic-site Bi catalysts gave a good selectivity for 4e− ORR and a corresponding half-wave potential of 0.875 V, approaching that of the best-known Fe/NC catalysts. This work presents new high-performance ORR catalysts based on the p-block-metal Bi, in contrast to the intensively studied d-block transition metals, and thus would provide new perspectives for developing PGM-free ORR catalysts. For oxygen reduction reaction (ORR), replacing the conventional electrocatalysts based on platinum-group metals (PGMs) with alternatives based on non-noble metals is vital for the large-scale applications of green energy conversion and chemical synthesis. Here, we report the discovery of ORR catalysts based on the p-block-metal bismuth (Bi); the selectivity in ORR pathways could be controlled by tailoring the size of Bi. Specifically, the metallic Bi nanoparticles gave a high selectivity (>96%) for 2e− ORR, an ultra-high kinetic current density (3.8 mA·cm−2 at 0.65 V), and an excellent stability; in contrast, the single-atomic-site Bi catalysts gave a good selectivity for 4e− ORR and a corresponding half-wave potential of 0.875 V, approaching that of the best-known Fe/NC catalysts. This work presents new high-performance ORR catalysts based on the p-block-metal Bi, in contrast to the intensively studied d-block transition metals, and thus would provide new perspectives for developing PGM-free ORR catalysts.

USc2C2 and USc2NC Clusters with U-C Triple Bond Character Stabilized Inside Fullerene Cages.

The chemistry of f-block metal-carbon multiple bonds is underdeveloped compared to well-established carbene complexes of the d-block transition metals. Herein, we report two new actinide-rare earth mixed metal carbides and nitrogen carbide cluster fullerenes, USc2C2@D5h(6)-C80 and USc2NC@D5h(6)-C80, which contain U-C bonds with triple bond character and were successfully synthesized and characterized by mass spectrometry, UV-vis-NIR spectroscopy, Fourier transform infrared spectroscopy, single crystal X-ray diffraction, and DFT calculations. Crystallographic studies show that the two previously unreported clusters, USc2C2 and USc2NC, are stabilized in the D5h(6)-C80 carbon cage and adopt unique trifoliate configurations, in which C2/NC units are almost vertically inserted into the plane defined by the U and two Sc atoms. Combined experimental and theoretical studies further reveal the bonding structure of USc2C2 and USc2NC, which contain C═U(VI)═C and C═U(V)═N bonding motifs. The electronic structures of the two compounds are determined as U6+(Sc2)6+(C4-)2@D5h(6)-C804- and U5+(Sc2)6+(N)3-(C)4-@D5h(6)-C804-, respectively. Quantum-chemical studies confirm that the U-C bonds in both molecules show unprecedented multicenter triple-bond character. The discovery of this unique U-C multiple bond offers a deeper understanding of the fundamentals of uranium chemistry.

Emerging d−d orbital coupling between non-d-block main-group elements Mg and I at high pressure

d-d orbital coupling, which increases anisotropic and directional bonding, commonly occurs between d-block transition metals. Here, we report an unexpected d-d orbital coupling in the non-d-block main-group element compound Mg2I based on first-principles calculations. The unfilled d orbitals of Mg and Iatoms under ambient conditions become part of the valence orbitals and couple with each other under high pressures, resulting in the formation of highly symmetric I-Mg-I covalent bonding in Mg2I, which forces the valence electrons of Mg atoms into the lattice voids to form interstitial quasi-atoms (ISQs). In turn, the ISQs highly interact with the crystal lattice, contributing to lattice stability. This study greatly enriches the fundamental understanding of chemical bonding between non-d-block main-group elements at high pressures.

One-Pot Size-Controlled Synthesis of Tin- and Antimony-Based Intermetallic Nanoparticles

Intermetallic nanoparticles show unique electronic, magnetic, and optical properties. Nonetheless, methods of their synthesis with both size and phase control are scarce, restricting exploration of these materials’ applications. We demonstrate synthetic protocols toward freestanding intermetallic nanoparticles consisting of d-block transition metals and p-block metals/metalloids, including CrSn2, MnSn2, FeSn2, MnSb, FeSb2, and CoSb. Reaction variables such as precursor type, temperature, reagent concentration, and reducing agent are all shown to affect the size and/or phase of the intermetallic nanoparticles. The ubiquity of these protocols is demonstrated by showing the magnetic characterization of MnSb nanoparticles as a function of both size and Mn/Sb stoichiometry. The synthetic protocols established here are expected to be readily adaptable to other intermetallic systems.

Luminescent Metal Complexes for Bioassays in the Near-Infrared (NIR) Region.

Near-infrared (NIR, 700-1700nm) luminescent imaging is an emerging bioimaging technology with low photon scattering, minimal autofluorescence, deep tissue penetration, and high spatiotemporal resolution that has shown fascinating promise for NIR imaging-guided theranostics. In recent progress, NIR luminescent metal complexes have attracted substantially increased research attention owing to their intrinsic merits, including small size, anti-photobleaching, long lifetime, and metal-centered NIR emission. In the past decade, scientists have contributed to the advancement of NIR metal complexes involving efforts to improve photophysical properties, biocompatibility, specificity, pharmacokinetics, in vivo visualization, and attempts to exploit new ligand platforms. Herein, we summarize recent progress and provide future perspectives for NIR metal complexes, including d-block transition metals and f-block lanthanides (Ln) as NIR optical molecular probes for bioassays.

Selective hydroboration of terminal alkynes catalyzed by heterometallic clusters with uranium–metal triple bonds

Selective hydroboration of terminal alkynes catalyzed by heterometallic clusters with uranium–metal triple bonds

Coordination-driven self-assemblies of two hetero‐trinuclear [Cu(II)2Ln(III)] (Ln = La and Ce) complexes with a flexible bis(salamo)‐type ligand

d-Block transition metal(II)-lanthanide(III) (3d-4f) hetero‐trinuclear [Cu(II)2Ln(III)] (Ln = La and Ce) complexes [Cu2La(L)(ƞ 2-NO3)3(CH3OH)2]·2CH3OH (1) and [Cu2Ce(L)(ƞ 2-NO3)3(CH3OH)2]·2CH3OH (2) are described, both of which are formed by a flexible symmetrical bis(salamo)-type ligand H4L. The two 3d-4f complexes have been synthesized and characterized by elemental analyses, IR spectra and UV–Vis spectroscopy. The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction analyses. In 1 and 2, each Cu(II) ion (Cu1 or Cu2) is located in the N2O2 cavity of an (L)4− unit, while the apex is occupied by one oxygen atom of the coordinated methanol molecule, forming a penta-coordinated square pyramidal geometry. The lanthanide(III) (La or Ce) ion is located in the O6-donor coordination sphere of the completely deprotonated (L)4− unit and coordinated with the other six oxygen atoms of the three nitrate ligands to form a twelve-coordinated icosahedron. At the same time, the supramolecular structures are formed by intermolecular hydrogen bonding interactions and quantitatively determined by Hirshfeld surfaces analyses. Fluorescence properties and DFT calculations of 1 and 2 were also studied.

Quaternary Noncentrosymmetric Rare-Earth Sulfides Ba4RE2Cd3S10 (RE = Sm, Gd, or Tb): A Joint Experimental and Theoretical Investigation.

Multinary rare-earth chalcogenides with d-block transition metals have attracted considerable attention owing to their intriguing structural architectures and promising practical applications. In this work, three quaternary rare-earth sulfides, Ba4RE2Cd3S10 (RE = Sm, Gd, or Tb), have been obtained by the high-temperature solid-state method. These compounds are isostructural and belong to the noncentrosymmetric orthorhombic space group Cmc21 (No. 36). The basic structural unit contains unique two-dimensional anionic [RE2Cd3S10]8- layers, which are separated by Ba2+ cations. Remarkably, Ba4Sm2Cd3S10 exhibits a high second-harmonic-generation intensity (1.8 times that of AgGaS2) and a significantly higher laser-induced damage threshold (14.3 times that of AgGaS2), which is the first case possessing an infrared (IR) nonlinear optical (NLO) property in the quaternary AE/RE/TM/Q (AE = alkaline-earth metals; RE = rare-earth metals; TM = d-block transition metals; and Q = chalcogen) systems. Moreover, theoretical investigations of the structure-property relationship indicate that the combined action of various types of NLO-active units makes the main contribution to the SHG activity. This discovery may shed light on broadening the frontiers of IR-NLO materials.

First-Row d-Block Element-Catalyzed Carbon-Boron Bond Formation and Related Processes.

Organoboron reagents represent a unique class of compounds because of their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation of the carbon-boron bond into a carbon-X (X = C, N, and O) bond in a stereocontrolled fashion has become invaluable in medicinal chemistry, agrochemistry, and natural products chemistry as well as materials science. Over the past decade, first-row d-block transition metals have become increasingly widely used as catalysts for the formation of a carbon-boron bond, a transformation traditionally catalyzed by expensive precious metals. This recent focus on alternative transition metals has enabled growth in fundamental methods in organoboron chemistry. This review surveys the current state-of-the-art in the use of first-row d-block element-based catalysts for the formation of carbon-boron bonds.