Metal-metal Bond Research Articles

Binuclear complexes of all first row 3d metals (Sc to Zn) with a cyclic N4-Tetradentate Ligand: Metal-Metal bond Strengths and bond orders

Metal-metal (MM) bonds in binuclear complexes M2L2 (L = tetradentate ligand) for the first row transition metals are studied using DFT to design novel complexes which mimic lantern complexes having four bidentate ligands. Two orientations for the ligand array are applied − orthogonal (orth) and lateral (lat). Ground states for all complexes are identified from several low-lying spin states, where each orth isomer is generally lower in energy than the corresponding lat isomer. All the MM bonds are assigned formal bond order (fBO) values through MO analysis and/or electron counting. The M2L2orth complexes in many ways mimic the geometrical and electronic structure of known tetragonal lantern complexes. The formal shortness ratio (FSR) and the Wiberg index WMM for the MM bond correlate well with the fBO values, validating their use as measures of intrinsic MM bond strength.

Mechanism and chemoselectivity of nitrile hydrosilylation catalyzed by [E-Rh] (E=Al, Ga, In) heterobimetallic catalysts: A theoretical perspective

Transition metals catalyzed hydrosilylation reaction is of significant values in organic synthesis. Herein the detailed mechanisms of the phenylacetonitrile hydrosilylation catalyzed by bimetallic [E-Rh] (E=Al, Ga, In) catalysts, as well as the RhCl(PPh3)3 monometallic catalyst, were investigated by DFT calculations. The electronic structure analysis indicates that the different atomic contributions of the Rh atom in E-Rh bond result in the polarity variations of the metal-metal bonds and different catalytic activities. The whole catalyzed cycle involves five processes: the formation of rhodium hydride complex, activation of H2SiMe2, insertion of phenylacetonitrile, reductive elimination, and isomerization. The reaction activities of [E-Rh] (E=Al, Ga, In) decrease successively, which is in agreement with the atomic contributions of Rh in three catalysts. DI analysis provides the evidence that the catalytic activity is controlled by the distortion energy of rate-determining state. QTAIM analysis shows the transformation of the Cl atom between two metal atoms, providing a clear description for structural changes in catalytic cycle.

Synthesis and Reactivity of an Alumanyl-Tin Species to Form an Al,N-Heteroallene Derivative.

The molecular chemistry of metal-metal bonds is crucial for understanding the bonding and reactivity of metal-containing molecules as well as solid metals and their alloys, especially with respect to their application as catalysts for organic transformations and industrial processes. Despite the high efficiency of the recently developed nucleophilic alumanyl anions in the synthesis of diverse Al-metal bonds, the bonding between main group metals in a low oxidation state and the Al atom remains largely unexplored. This paper describes the reaction of an alumanyl anion with a chlorostannylene precursor to afford a compound with an unprecedented covalent Al-Sn bond. The lability of the covalent Al-Sn bond renders it reactive toward the insertion of carbodiimide, N2O, and phenylacetylene. Remarkably, the reaction with benzonitrile furnished an unprecedented Al,N-heteroallene species that contains a linear Al═N═C linkage.

Prediction of Covalent Metal-Metal Bonding in Cp-M-M'-Nacnac Complexes of Group 2 and 12 Metals (Be, Mg, Ca, Zn, Cd, Hg).

Bimetallic CpMM'Nacnac molecules with group 2 and 12 metals (M=Be, Mg, Ca, Zn, Cd, Hg) that contain novel metal-metal bonding have been investigated in a theoretical study of their molecular and electronic structure, thermodynamic stability, and metal-metal bonding. In all cases the metal-metal bonds are characterized as electron-sharing covalent single bonds from natural bond orbital (NBO) and energy-decomposition analysis with natural orbitals of chemical valence (EDA-NOCV) analysis. The sum of [MM'] charges is relatively constant, with all complexes exhibiting a [MM']2+ core. Quantum theory of atoms in molecules (QTAIM) analysis indicates the presence of non-nuclear attractors (NNA) in the metal-metal bonds of the BeBe, MgMg, and CaCa complexes. There is substantial electron density (0.75-1.33 e) associated with the NNAs, which indicates that these metal-metal bonds, while classified as covalent electron-sharing bonds, retain significant metallic character that can be associated with reducing reactivity of the complex. The predicted stability of these complexes, combined with their novel covalent metal-metal bonding and potential as reducing agents, make them appealing targets for the synthesis of new metal-metal bonds.

CaY@C2n: Exploring Molecular Qubits with Ca-Y Metal-Metal Bonds.

Metal-metal bonding is crucial in chemistry for advancing our understanding of the fundamental aspects of chemical bonds. Metal-metal bonds based on alkaline-earth (Ae) elements, especially the heavier Ae elements (Ca, Sr, and Ba), are rarely reported due to their high electropositivity. Herein, we report two heteronuclear di-EMFs CaY@Cs(6)-C82 and CaY@C2v(5)-C80, which contain unprecedented single-electron Ca-Y metal-metal bonds. These compounds were characterized by single-crystal X-ray crystallography, electron paramagnetic resonance (EPR) spectroscopy, and DFT calculations. The crystallographic study of CaY@Cs(6)-C82 shows that Ca and Y are successfully encapsulated into the carbon cage with a Ca-Y distance of 3.691 Å. The CW-EPR study of both CaY@Cs(6)-C82 and CaY@C2v(5)-C80 exhibits a doublet, suggesting the presence of an unpaired electron located between Ca and Y. The combined experimental and theoretical results confirm the presence of a Ca-Y single-electron metal-metal bond with substantial covalent interaction, attributed to significant overlap between the 4s4p orbitals of Ca and the 5s5p4d orbitals of Y. Furthermore, pulse EPR spectroscopy was used to investigate the quantum coherence of the electron spin within this bond. The unpaired electron, characterized by its s orbital nature, is effectively protected by the carbon cage, resulting in efficient suppression of both spin-lattice relaxation and decoherence. CaY@Cs(6)-C82 behaves as an electron spin qubit, displaying a maximum decoherence time of 7.74 μs at 40 K. This study reveals an unprecedented Ae-rare-earth metal-metal bond stabilized by the fullerene cages and elucidates the molecular qubit properties stemming from their unique bonding character, highlighting their potential in quantum information processing applications.

Deeply Reduced Chiral MoIV6-Polyoxometalates with Highly Enhanced Electronic Conductivity.

A series of deeply reduced MoIV6-polyoxometalates (POMs), [MoIV6(bpy)6MoVI2O16S2]·10H2O (1) (bpy = 2,2'-bipyridine), [MoIV6(bpy)4(L-TrA)2MoV4(bpy)2O14S4]2·36.5H2O (2), and [MoIV6(bpy)4(D-TrA)2MoV4(bpy)2O14S4]2 (3) (TrA = tartaric acid), were obtained from one-pot hydrothermal syntheses. They feature the bioxo-bridged [MoIV3O3S]4+ incomplete cuboidal cores stabilized by strong triangular metal-metal bonds and datively chelated bpy π-ligands. The two apical MoVIO4 in 12e-Mo8 (1) and two [MoV2O3STrAbpy] in 16e-Mo10 (2, 3) complete the octahedral coordination geometry of the deeply reduced MoIV, not counting the MoIV-MoIV d2-d2 bonds. The aromatic planar bpy π ligands form a two-dimensional face-to-face π stacking supramolecular structure, which are further strengthened by point-to-face C-H···π interactions in the π stacked layers. 16e-Mo10 (2, 3) has stronger intramolecular face-to-face π stacking interactions, which are interconnected by intermolecular C-H···π into a three-dimensional framework structure. These structural features account for their highly enhanced electronic conductivities (1, 6.19 × 10-8 S cm-1; 2, 2.18 × 10-7 S cm-1), providing a new way of thinking to improve electronic conductivity of POMs. 1-3 have been described by first-principles density function theory (DFT) calculations and also characterized by elemental analyses, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), solid UV-visible spectra, and circular dichroic (CD) spectra.

Measuring the Magnetic Anisotropy of Metal-Metal Multiple Bonds: The Importance of Correcting for Ligand Effects.

We describe the synthesis and characterization of the quadruply-bonded dimer Mo2(CH2NMe2BH3)4 in which each molybdenum(II) center is bound to two chelating boranatodimethylaminomethyl (BDAM) ligands. The BDAM anions bind to the metal at one end by a metal-carbon σ bond and at the other by a three-center M-H-B interaction. Each BDAM ligand chelates to a single Mo atom so that the metal-metal bond is unbridged; the Mo-Mo distance is 2.114(2) Å. Structural and solution NMR data, analyzed via McConnell's equation and supported by DFT calculations, show that the magnetic anisotropies associated with highly polarizable and π-bonding ligands (such as chloride groups and aryl rings) can greatly affect the NMR chemical shifts of reporter groups, so that ignoring their contributions leads to significant overestimates of the anisotropy due just to the metal-metal bond. We propose a method to quantify and correct for the magnetic anisotropy effects arising from the ligands. Application of this method to Mo2(BDAM)4 indicates that the magnetic anisotropy of the Mo-Mo quadruple bond in this molecule is about -800 × 10-36 m3 molecule-1. Anisotropies significantly higher than this value (as sometimes reported in the prior literature) are most likely incorrect.

N,C,N-Pincers in Platinum Bimetallic Complexes: Influence of the Pincer and Bridging Ligands on the Metal-Metal Bond and the Photophysical Properties.

Precursors PtCl{κ3-N,C,N-[py-C6HMe2-py]} (1), PtCl{κ3-N,C,N-[py-O-C6H3-O-py]} (2), Pt(OH){κ3-N,C,N-[py-C6HMe2-py]} (3), and Pt(OH){κ3-N,C,N-[py-O-C6H3-O-py]} (4) were used to prepare d8-platinum bimetallic complexes. Precursors 1 and 2 react with AgBF4 and 7-azaindole (Haz) to give [Pt{κ3-N,C,N-[py-C6HMe2-py]}{κ1-N-[Haz]}]BF4 (5) and [Pt{κ3-N,C,N-[py-O-C6H3-O-py]}{κ1-N-[Haz]}]BF4 (6) and 3 and 4 with indolo[2,3-b]indole (H2ii) to generate Pt{κ1-N-[Hii]}{κ3-N,C,N-[py-C6HMe2-py]} (7) and Pt{κ1-N-[Hii]}{κ3-N,C,N-[py-O-C6H3-O-py]} (8). Subsequent addition of 3 and 4 to 5-7 affords bimetallic derivatives [{Pt[κ3-N,C,N-(py-C6HMe2-py)]}2{μ-N,N-[az]}]BF4 (9), [{Pt[κ3-N,C,N-(py-O-C6H3-O-py)]}2{μ-N,N-[az]}]BF4 (10), and {Pt[κ3-N,C,N-(py-C6HMe2-py)]}2{μ-N,N-[ii]} (11). X-ray structures of 9-11 reveal separations between the metals in sequence 9 (3.0515(4) Å) < 10 (3.2689(9) Å) < 11 (3.2949(2) Å). DFT calculations support σ overlap of the dz2 orbitals of platinum atoms, for 9 and 10. Accordingly, their absorption spectra show a MMLCT transition. Complex 9 is a red emitter. The excited state has 3MMLCT characteristics and a Pt-Pt separation of 2.763 Å. Complex 11 is a dual emitter in the red and NIR regions, in solid. Both excited states have a 3LC/LMCT characteristic and platinum-platinum separations of 3.290 and 3.202 Å. Intermediate 5 is a green emitter that achieves quantum yields close to unity, when diluted in PMMA and 1,2-dichloroethane at low concentrations.

Antiferromagnetic Interactions through the Thirteen Å Metal-Metal Distances in Heterometallic One-Dimensional Chains.

A heterometallic and paramagnetic one-dimensional aligned chain in -Rh(+2)-Rh(+2)- Pt(+2)-Ni(+2)-Pt(+2)- with direct metal-metal bonds was obtained via HOMO-LUMO interactions at the σ* (dz2) orbital between [Rh2(O2CCH3)4] and [Pt2Ni(piam)4(NH3)4] (piam=pivalamidate). The one-dimensional chains had straight backbones attributed to face-to-face stacking of each complex, and the Ni atoms were separated by approximately 13 Å from four different metals. Each Ni atom had two unpaired electrons in the d-orbitals, which strongly exchanged with J=-37.9 cm-1 through the diamagnetic -Pt-Rh-Rh-Pt- bonds.

Binuclear Lantern Complexes of All First-Row 3d Metals Scandium to Zinc: Metal-Metal Bond Lengths and Bond Orders, with Measures of Intrinsic Metal-Metal Bond Strength.

The B3LYP and M06-L functionals with the cc-pVTZ basis set are used to study lantern-type binuclear complexes of all the first-row (3d block) metals scandium to zinc in various low-energy spin states, out of which the ground states are predicted. These complexes are studied as models using mostly the unsubstituted formamidinate ligand. For each metal, metal-metal (MM) bond lengths are related to the formal MM bond orders (zero to five), derived by MO analysis and by electron counting. The predicted ground-state spin multiplicities and MM bond lengths of the model complexes generally agree fairly well with available experimental results on substituted analogues. Finally, values of the formal shortness ratio and Wiberg index for the MM bonds in all of these complexes in all spin states studied are categorized into ranges according to the MM bond orders 0 to 5 in steps of 0.5. The trends shown validate their use in estimating intrinsic metal-metal bond strength regardless of the metal.

Dicarbonyl-1κ2 C-μ-chlorido-2:3κ2 Cl:Cl-penta-chlorido-2κ2 Cl,3κ3 Cl-[1(η6)-toluene]digallium(III)ruthenium(I)(Ru-Ga).

The title compound, [RuGa2Cl6(C7H8)(CO)2] or [(CO)2(GaCl2)(η6-toluene)Ru]+[GaCl4]-, was isolated from the reaction of Ga2Cl4 with di-phenyl-silanediol in toluene, followed by the addition of Ru3(CO)12. The compound contains a ruthenium-gallium metal-metal bond with a length of 2.4575 (2) Å.

Trans-Di-aqua-tetra-kis-(tetra-hydro-furan-κO)iron(II) μ-carbonyl-tetra-deca-carbonyl-tetra-chlorido-μ-di-methyl-silanediolato-tetra-galliumtetra-iron(7 Ga-Fe)(Fe-Fe) tetra-hydro-furan tetrasolvate.

The title compound, [Fe(C4H8O)4(H2O)2][Fe4Ga4(C2H6O2Si)Cl4(CO)15]·4C4H8O, consists of an iron(II) cation octa-hedrally coordinated by two water mol-ecules (trans) with four tetra-hydro-furans (THF) at equatorial sites. Two additional THF mol-ecules are hydrogen bonded to each of the water mol-ecules. The dianion of the title compound is an organometallic butterfly complex with a dimethyl siloxane core and two iron-gallium fragments. The lengths of the iron to gallium metal-metal bonds range from 2.3875 (6) to 2.4912 (6) Å.

Conversion of Methane at Room Temperature Mediated by the Ta-Ta σ-Bond.

Metal-metal bonds constitute an important type of reactive centers for chemical transformation; however, the availability of active metal-metal bonds being capable of converting methane under mild conditions, the holy grail in catalysis, remains a serious challenge. Herein, benefiting from the systematic investigation of 36 metal clusters of tantalum by using mass spectrometric experiments complemented with quantum chemical calculations, the dehydrogenation of methane at room temperature was successfully achieved by 18 cluster species featuring σ-bonding electrons localized in single naked Ta-Ta centers. In sharp contrast, the other 18 remaining clusters, either without naked Ta-Ta σ-bond or with σ-bonding electrons delocalized over multiple Ta-Ta centers only exhibit molecular CH4-adsorption reactivity or inertness. Mechanistic studies revealed that changing cluster geometric configurations and tuning the number of simple inorganic ligands (e.g., oxygen) could flexibly manipulate the presence or absence of such a reactive Ta-Ta σ-bond. The discovery of Ta-Ta σ-type bond being able to exhibit outstanding activity toward methane conversion not only overturns the traditional recognition that only the metal-metal π- or δ-bonds of early transition metals could participate in bond activation but also opens up a new access to design of promising metal catalysts with dual-atom as reactive sites for chemical transformations.

Combinatorial investigation on corrosion resistance of Ir-Ni-Ta alloys

Metallic glasses are often considered to exhibit remarkable corrosion resistance. However, the respective roles of chemical composition and amorphous structure remain unclear. In this work, we take Ir-Ni-Ta alloy system as a model system and utilize combinatorial fabrication and high-throughput characterizations to reveal the correlations between alloy composition and corrosion current density and corrosion potential. The results indicate strong correlations of corrosion current density with metal-metal bond strength and metal-oxygen bond strength, suggesting that the corrosion of the Ir-Ni-Ta metallic glasses is primarily controlled by chemical composition. However, an amorphous structure can facilitate the formation of denser passive film, and thus superimpose a positive influence on alloys that inherently exhibit corrosion resistance. Our findings would help the designing metallic glasses of superior corrosion resistance.

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.

Tuning Photoredox Catalysis of Ruthenium with Palladium: Synthesis of Heterobimetallic Ru-Pd Complexes That Enable Efficient Photochemical Reduction of CO2.

New Ru-Pd heterobimetallic complexes were synthesized and structurally characterized utilizing 6,6″-bis(phosphino)-2,2':6',2″-terpyridine as a scaffold for the metal-metal bond. The dicationic Ru-Pd complex was found to exhibit high catalytic activity as a photocatalyst for photochemical reduction of CO2 to CO under visible light irradiation. This study established a new design of transition metal catalysts that tune photoredox catalysis with metalloligands.

Dihydrogen Cleavage by a Zinc-Zinc Bond of a Heteroleptic Dizinc(I) Cation.

Oxidative addition of dihydrogen across a metal-metal bond to form reactive metal hydrides in homogeneous catalysis is known for transition metals but not for zinc(I)-zinc(I) bond as found in Carmona's eponymous dizinconene [Zn2Cp*2] (Cp* = η5-C5Me5). Dihydrogen reacted with the heteroleptic zinc(I)-zinc(I) bonded cation [(L2)Zn-ZnCp*][BAr4F] (L2 = TMEDA, N,N,N',N'-tetramethylethylenediamine, TEEDA, N,N,N',N'-tetraethylethylenediamine; ArF = 3,5-(CF3)2C6H3) under 2 bar at 80 °C to give the zinc(II) hydride cation [(L2)ZnH(thf)][BAr4F] along with zinc metal and Cp*H derived from the intermediate [Cp*ZnH]. DFT calculations show that the cleavage of dihydrogen occurs through a highly unsymmetrical transition state. Mechanistic studies agree with a heterolytic cleavage of dihydrogen as a result of the cationic charge and unsymmetrical ligand coordination. To explore the existence of zinc(I) hydride, thermally unstable hydridotriphenylborate complexes of zinc(I) [(L2)Zn(HBPh3)-ZnCp*] (L2 = TMEDA, TEEDA; TMPDA, N,N,N',N'-tetramethyl-1,3-propylenediamine) have been prepared by salt metathesis and were shown to undergo fast exchange with both BPh3 and [HBPh3]-.

Synergistic effects of β-NaFeO2 ferrite nanoparticles for photocatalytic degradation, antibacterial, and antioxidant applications.

Here, synthesis and thorough characterization of β-NaFeO2 nanoparticles utilizing a co-precipitation technique is presented. XRD analysis confirmed a hexagonal-phase structure of β-NaFeO2. SEM revealed well-dispersed spherical nanoparticles with an average diameter of 45 nm. The FTIR spectrum analysis revealed weak adsorption bands at 1054 cm-1 suggested metal-metal bond stretching (Fe-Na). UV-Visible spectroscopy indicates a 4.4 eV optical band gap. Colloidal stability of β-NaFeO2 was evidenced via Zeta potential (-28.5 mV) and Dynamic Light Scattering (DLS) measurements. BET analysis reveals a substantial 343.27 m2 g-1 surface area with mesoporous characteristics. Antioxidant analysis indicates efficacy comparable to standard antioxidants, while concentration-dependent antibacterial effects suggest enhanced efficacy against Gram-positive bacteria, particularly Streptococcus. The Photocatalytic activity of β-NaFeO2 showed significant pollutant degradation (>90% efficiency), with increased degradation rates at higher nanoparticle concentrations, indicating potential for environmental remediation applications.

Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions.

Previous studies on bimetallic paddlewheel compounds have established a direct correlation between metal-metal distance and ligand torsion angles, leading to the rule that higher torsion results in longer metal-metal bond distances. Here, the new discovery based on diarylformamidinateRu₂⁵⁺ paddlewheel compounds [Ru2Cl(DArF)4]that show an opposite behavior is reported: higher torsions lead to shorter metal-metal distances. This discovery challenges the assumption that internal rotation solely impacts the δ bond. By combining experimental and theoretical techniques, it is demostrated that this trend is associated with previously overlooked π metal-ligand interactions. These π metal-ligand interactions are a direct consequence of the paddlewheel structure and the conjugated nature of the bidentate ligands. This findings offer far-reaching insights into the influence of equatorial ligands and their π-conjugation characteristics on the electronic properties of paddlewheel complexes. That this effect is not exclusive of diruthenium compounds but also occurs in other bimetallic cores such as ditungsten or dirhodium is demonstrated, and with other ligands showing allyl type conjugation. These results provide a novel approach for fine-tuning the properties of these compounds with significant implications for materials design.

Green Synthesis of Ag-Doped CuO Nanocomposites Using Honey Solution for Evaluation of their Antimicrobial and Antioxidant Activities

Background: The rise of infectious diseases especially due to drug-resistant microbes and free radicals has caused a serious threat to public health worldwide. Green synthesized nanomaterials (NMs) have emerged as promising candidates to minimize the damage due to these problems. Doping the bioactive and stable silver atom into the biocompatible CuO by capping the nanoparticles with phytochemicals from honey enhanced the biological activity. The present study aimed to synthesize Ag- CuO NCs using the honey solution for antimicrobial and antioxidant activity evaluation. Methods: The nanoparticles (NPs) and nanocomposites (NCs) were successfully synthesized using the honey solution and characterized by spectroscopic techniques such as XRD, UV-Vis, FTIR, and SEM. The role of the secondary metabolites in honey solution is to stabilize the fabricated NMs by capping. Results: The red shift observed with the addition of Ag dopant indicates the narrowing of the CuO band gap. FT-IR characterization confirmed the presence of various functional group bands in the synthesized NMs. The spectral band between 900–500 cm−1 displays the presence of metal-oxygen and metal-metal bonds, confirming the production of pure CuO NPs and Ag-CuO NCs. The fabricated CuO NPs and Ag-CuO NCs have crystalline structures with crystallite sizes of 14.14 and 17.40 nm respectively. SEM data showed that CuO NPs are spherical and Ag-CuO NCs have a mixture of spherical and cubic shapes. The NMs displayed concentration-dependent biological activities. Conclusion: The successful incorporation of silver into the crystal lattice of CuO integrated with the presence of secondary metabolites on the surface improved the potential. Hence, the prepared NMs may have pharmaceutical applications in the future with some modifications for the enhancement of their potential.