Metal Cluster Complexes Research Articles

Biomimetic Transition Metal Cluster Complexes: Synthetic Studies and Applications in the Reduction of Inert Small Molecules

Abstract Transition metal cluster complexes, particularly those containing iron and sulfur, are used as catalysts for the biological reduction of inert small molecules such as N2 and CO2. The structures of these biological clusters are complicated and the protein backbones around the clusters often play important roles in catalysis, hence reproducing or mimicking the enzymatic functions with synthetic cluster complexes remains a challenge. Appropriate assumptions and hypotheses on the relationships between the structures and functions of biological clusters are needed to develop synthetic molecular catalysts inspired by enzymes. This account reviews recent studies by the author and his coworkers on iron-containing biomimetic cluster complexes. Cubic Mo-Fe-S clusters supported by bulky cyclopentadienyl ligands on molybdenum were designed and synthesized, and their Fe sites captured and catalytically converted N2 under reducing conditions. Iron-hydride clusters, which are relevant to the active species of biological and industrial nitrogen fixation, also served as catalysts for the reduction of N2. Furthermore, various metal-sulfur clusters, ranging from a structural mimic of the complex active site of the N2-reducing enzyme to a simple and cubic [Fe4S4] cluster, were found to catalyze the biologically inaccessible direct conversion of CO2 to short-chain hydrocarbons. These studies have demonstrated the potential utility of biomimetic approaches to the catalytic reduction of inert small molecules, through the rational design and synthesis of simple yet appropriate iron-containing cluster complexes.

Palladium cluster complex [Pd13(μ4-C7H7)6]2+ (C7H7 = tropylium) with an fcc-close-packed cuboctahedral Pd13 core and isomers: theoretical insight into ligand-control of the Pd13 core structure.

One of the challenging targets in today's chemistry is size-, shape- and metal-atom packing-controlled synthesis of nano-scale transition metal cluster complexes because key factors governing these features have been elusive. Here, we present a DFT study on a recently synthesized palladium cluster complex [Pd13(μ4-C7H7)6]2+ (named Cubo-μ4; C7H7 = tropylium) with an fcc-close-packed cuboctahedral Pd13 core and possible isomers. The stability decreases in the order Cubo-μ4 > [Pd13(μ3-C7H7)3(μ4-C7H7)3]2+ with an hcp-close-packed anticuboctahedral Pd13 core (Anti-μ3,4) > [Pd13(μ3-C7H7)6]2+ with a non-close packed icosahedral Pd13 core (Ih-μ3) > [Pd13(μ4-C7H7)6]2+ with an anticuboctahedral Pd13 core (Anti-μ4) > [Pd13(μ3-C7H7)6]2+ with a cuboctahedral Pd13 core (Cubo-μ3). This ordering disagrees with the stability of the Pd13 core. The key factor governing the stability and metal-atom packing manner of these Pd13 cluster complexes is not the stability of the Pd13 core but the interaction energy between the Pd13 core and the [(C7H7)6]2+ ligand shell. The interaction energy is mainly determined by the charge-transfer from the Pd13 core to the [(C7H7)6]2+ ligand shell and the coordination mode of the C7H7 ligand (μ3- vs. μ4-coordination bond). In the μ4-coordination, all seven C atoms of the C7H7 ligand interact with four Pd atoms of the Pd4 plane using two CC double bonds and one π-allyl moiety. On the other hand, in the μ3-coordination, one or two C atoms of C7H7 cannot form bonding interaction with the Pd atom of the Pd3 plane. Thus, the use of appropriate capping ligands is one of the key points in the synthesis of nano-scale metal cluster complexes.

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

Selective formation of dinuclear and heptanuclear Zn(II), Ni(II), and Co(II) metal clusters from a simple dialdehyde

Herein, the selective formation of dinuclear and hexagonal disk-shape heptanuclear metal cluster complexes is reported. The reaction of 4-tert-butyl-2,6-diformylphenol (L) and M(ClO4)2, where M is Zn (II), Co (II), or Ni (II), in the presence of a strong base resulted in the formation of heptanuclear metal cluster complexes. Treatment of M(ClO4)2·6H2O (M = Zn, and Ni) in the presence of NaOCH3 in MeOH at the elevated temperature afforded [Zn2(L)2(CH3O)4].ClO4 (1) and [Ni2(L)2(CH3O)2].ClO4 (2). Furthermore, treatment of M(ClO4)2·6H2O (M = Zn, Co, and Ni) in the presence of NaOH in MeOH at the elevated temperature yielded heptanuclear metal cluster complexes [Zn7(L)6(µ3-CH3O)6]·2ClO4 (3), [Co7(L)6(µ3-CH3O)6]·2ClO4 (4), and [Ni7(L)6(µ3-OH)6]·2ClO4 (5). These were characterized using elemental analysis, infrared spectroscopy, and X-ray crystallography. Zinc complexes 1 and 3 were also characterized using 1H NMR spectroscopy. In the crystal structures of heptanuclear cluster complexes 3–5, six ligand molecules were aligned to hold six metal centers that were in hexagonal positions. The central metal atom was connected by the bridging of the oxygen atom of methoxy and hydroxy groups with the remaining metal atoms. The photophysical properties of complexes were studied and zinc complexes 1 and 3 showed strong fluorescence in PL spectra. Themetal cluster complexes 1, 3 and 4 were employed as catalysts in the cycloaddition reaction of CO2 to epoxide, exhibiting moderate activities.

Direct observation of x-ray excited optical luminescence from a Re6 metal cluster in true aqueous solution: The missing link between material characterization and in vivo applications

Phosphorescent octahedral metal cluster complexes are highly attractive in terms of biomedical applications, particularly in the area of luminescent diagnostics and photodynamic therapy (PDT). The ability of clusters to be excited by x-radiation followed by red/near infrared emission makes them a new promising class of photosensitizers for deep-PDT. This work demonstrates a direct observation of x-ray-excited optical luminescence of hexanuclear clusters, by example of rhenium cluster complex Na4[{Re6Se8}(CN)6], in a true aqueous solution. The article also describes point-by-point the details and pitfalls of studying cluster radioluminescence in aqueous solution.

α-Pyridinyl Alcohols, α,α'-Pyridine Diols, α-Bipyridinyl Alcohols, and α,α'-Bipyridine Diols as Structure Motifs Towards Important Organic Molecules and Transition Metal Complexes.

The preparation and use of pyridinyl alcohols as ligands showed incredible increment in the past three decades. Important property of pyridinyl alcoholato ligands is their strong basicity, which is mainly due to the lack of resonance stabilization of the corresponding anion. This strongly basic anionic nature gives them high ability to make bridges between metal centers rather than to bind to only one metal center in a terminal fashion. They are needed as ligands due to their ability to interact with transition metals both covalently (with oxygen) and hemilabile coordination (through nitrogen). The review focuses on the wide application of α-pyridinyl alcohols, α,α'-pyridine diols, α- bipyridinyl alcohols, and α,α'-bipyridine diols as structure motifs in the preparation of important organic molecules which is due to their strongly basic anionic nature. It is clear from the review that in addition to their synthetic utility in the homogeneous and asymmetric catalytic reactions, the preparation of the crown ethers, cyclic and acyclic ethers, coordinated borates (boronic esters), pyridinyl-phosphine ligands, pyridinyl-phosphite ligands, and pyridinyl-phosphinite ligands is the other broad area of application of pyridinyl alcohols. In addition to the aforementioned applications they are used for modeling mode of action of enzymes and some therapeutic agents. Their strongly basic anionic nature gives them high ability to make bridges between metal centers rather than to bind to only one metal center in a terminal fashion in the synthesis of transition metal cluster complexes. Not least numbers of single molecule magnets that can be used as storage of high density information were the result of transition metal complexes of pyridinyl alcoholato ligands.

Neutral Chalcogenide Tungsten Cluster with Tris(2‐Cyanoethyl)phosphine

Despite the great prospects for the use of octahedral metal cluster complexes in various fields, chalcogenide tungsten compounds with functional organic ligands have practically not been studied. In this work, we present the synthesis and detailed characterization of a tungsten cluster with tris(2‐cyanoethyl)phosphine [{W6S8}(P(C2H4CN)3)6]. The compound has been obtained directly from (Bu4N)2[{W6Cl8}Cl6] in one step with a good yield. The crystal structure, determined by single‐crystal X‐ray diffraction analysis, as well as multinuclear NMR analysis have well confirmed the formation of the chalcogenide neutral cluster. Moreover, the electrochemical properties of the complex have been studied.

DNA Modified with Boron⁻Metal Cluster Complexes [M(C₂B₉H11)₂]-Synthesis, Properties, and Applications.

Together with tremendous progress in biotechnology, nucleic acids, while retaining their status as “molecules of life”, are becoming “molecular wires”, materials for the construction of molecular structures at the junction between the biological and abiotic worlds. Herein, we present an overview of the approaches for incorporating metal centers into nucleic acids based on metal–boron cluster complexes (metallacarboranes) as the metal carriers. The methods are modular and versatile, allowing practical access to innovative metal-containing DNA for various applications, such as nucleic acid therapeutics, electrochemical biosensors, infrared-sensitive probes, and building blocks for nanoconstruction.

Materials based on X-ray contrast octahedral metal cluster complexes and hydrophilic polymers

Herein we report the comparative study of cytotoxicity of a series of hexarhenium cluster complexes of general formula [{Re6Q8}L6]n (Q = S, Se, Te; L = P(CH2CH2COO–)3, SO32–, OH–, CN–) in the presence of hydrophilic polymers: dextran-70 (Mw ∼70 kDa) and polyethylene glycol (Mw ∼40 kDa) and their oxidised derivatives. It was demonstrated that cluster complexes in the presence of dextran polymers are generally more cytotoxic than non-coated cluster complexes, while PEG-coated cluster complexes are vice versa less cytotoxic.

Opening of Carborane Cages by Metal Cluster Complexes: The Reaction of a Thiolate-Substituted Carborane with Triosmium Carbonyl Cluster Complexes

The reaction of Os3(CO)10(NCMe)2 with closo-o-(1-SCH3)C2B10H11 has yielded the complex Os3(CO)9[μ3-η(3)-C2B10H9(SCH3)](μ-H)2, 1, by the loss of the two NCMe ligands and one CO ligand from the Os3 cluster and the coordination of the sulfur atom and the activation of two B-H bonds with transfer of the hydrogen atoms to the cluster. Reaction of 1 with a second equivalent of Os3(CO)10(NCMe)2 yielded the complex Os3(CO)9(μ-H)[(μ3-η(3)-1,4,5-μ3-η(3)-6,10,11-C2B10H8S(CH3)]Os3(CO)9(μ-H)2, 2, that contains two triosmium triangles attached to the same carborane cage. The carborane cage was opened by cleavage of two B-C bonds and one B-B bond. The B-H group that was pulled out of the cage became a triply bridging group on one of the Os3 triangles but remains bonded to the cage by two B-B bonds. When heated to 150 °C, 2 was transformed into the complex Os3(CO)9(μ-H)[(μ3-η(3)-μ3-η(3)-C2B10H7S(CH3)]Os3(CO)9(μ-H), 3, by the loss of two hydrogen atoms and a rearrangement that led to further opening of the carborane cage. Reaction of 1 with a second equivalent of closo-o-(1-SCH3)C2B10H11 has yielded the complex Os3(CO)6)(μ3-η(3)-C2B10H9-R-SCH3) (μ3-η(3)-C2B10H10-S-SCH3)(μ-H)3, 4a, containing two carborane cages coordinated to one Os3 cluster. Compound 4a was isomerized to the compound Os3(CO)6(μ3-η(3)-C2B10H9-R-SCH3)(μ3-η(3)-C2B10H10-R-SCH3)(μ-H)3, 4b, by an inversion of stereochemistry at one of the sulfur atoms by heating to 174 °C.

Phosphorescent PtAu2 Complexes with Differently Positioned Carbazole-Acetylide Ligands for Solution-Processed Organic Light-Emitting Diodes with External Quantum Efficiencies of over 20.

The utilization of phosphorescent metal cluster complexes as new types of emitting materials in organic light-emitting diodes (OLEDs) is becoming an alternative and viable approach for achieving high-efficiency electroluminescence. We report herein the design of cationic PtAu2 cluster complexes with differently positioned 9-phenylcarbazole-acetylides to serve as phosphorescent emitters in OLEDs. The rigid structures of PtAu2 complexes cause intense phosphorescence with quantum yields of over 85%, which originates from (3)[π(phenylcarbazole-acetylide) → π*(dpmp)] ligand-to-ligand and (3)[π(phenylcarbazole-acetylide) → p/s(PtAu2)] ligand-to-metal charge-transfer triplet excited states. When 8 wt % PtAu2 is doped to blended host materials of TCTA and OXD-7 (2:1 weight ratio) as light-emitting layers, solution-processed OLEDs give a current efficiency of 78.2 cd A(-1) and an external quantum efficiency (EQE) of 21.5% at a practical luminance of 1029 cd m(-2) with a slow efficiency roll-off upon increasing luminance. This represents the best device performance and the highest efficiency recorded at practical luminance for solution-processed OLEDs.

Cage Opening of a Carborane Ligand by Metal Cluster Complexes.

The reaction of Os3 (CO)10 (NCMe)2 with closo-o-C2 B10 H10 has yielded two interconvertible isomers Os3 (CO)9 (μ3 -4,5,9-C2 B10 H8 )(μ-H)2 (1 a) and Os3 (CO)9 (μ3 -3,4,8-C2 B10 H8 )(μ-H)2 (1 b) formed by the loss of the two NCMe ligands and one CO ligand from the Os3 cluster. Two BH bonds of the o-C2 B10 H10 were activated in its addition to the osmium cluster. A second triosmium cluster was added to the 1 a/1 b mixture to yield the complex Os3 (CO)9 (μ-H)2 (μ3 -4,5,9-μ3 -7,11,12-C2 B10 H7 )Os3 (CO)9 (μ-H)3 (2) that contains two triosmium triangles attached to the same carborane cage. When heated, 2 was transformed to the complex Os3 (CO)9 (μ-H)(μ3 -3,4,8-μ3 -7,11,12-C2 B10 H8 )Os3 (CO)9 (μ-H) (3) by a novel opening of the carborane cage with loss of H2 .

ChemInform Abstract: Topological Motifs in Cyanometallates: From Building Units to Three‐Periodic Frameworks

AbstractReview: 314 refs.

Photoluminescent materials based on PMMA and a highly-emissive octahedral molybdenum metal cluster complex

Transparent yet photoluminescent, materials with facile processability are key in many applications.

Topological Motifs in Cyanometallates: From Building Units to Three-Periodic Frameworks.

This review focuses on topological features of three-periodic (framework) p, d, and f metal cyano complexes or cyanometallates, i.e. coordination compounds, where CN(-) ligands play the main structure-forming role. In addition, molecular, one-periodic (chain), and two-periodic (layer) cyanometallates are considered as possible building blocks of the three-periodic cyanometallates. All cyanometallates are treated as systems of nodes (mononuclear, polynuclear, or transitional metal cluster complexes) joined together via CN-containing spacers. The most typical nodes and spacers as well as methods of their connection are described and systematized. Particular attention is paid to the overall structural motifs in the three-periodic cyanometallates, especially to the relations between the local coordination (coordination figure) of structural units and the entire framework topology. The chemical factors are discussed that influence the cyanometallate topological properties due to modification of nodes, spacers, or coordination figures.

Application of noble metal cluster to PMMA resin and influence on mechanical properties and color.

To improve the mechanical strength of denture base resin, several types of noble metal cluster were introduced into PMMA, and the mechanical properties and color changes were evaluated. Complex salts of gold, silver, platinum, and palladium were used as the raw materials of noble metal clusters, and after adding each cluster to MMA, polymerization and thermal treatment were performed to produce PMMA-noble metal cluster complexes. Bending deflection, bending strength, and Vickers hardness were measured, and the formation conditions of metal clusters were investigated using EPMA, SEM, and TEM. Furthermore, color changes between before and after metal cluster creation were measured. The bending deflection increased with the addition of silver and platinum, and decreased with the addition of palladium. The bending strength was lowest with the addition of gold, highest with the addition of palladium. Vickers hardness increased with the addition of palladium. Color differences increased with increasing thermal treatment temperature.

Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

Comproportionation reactions of rare-earth metal trihalides (RX3) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ({T3R11}X15-type, P63/m), tetramers ({T4R16}X28{R4} (P-43m), {T4R16}X20 (P42/nnm), {T4R16}X24(RX3)4 (I41/a) and {T4R16}X23 (C2/m) types of structure) and pentamers ({Ru5La14}2Br39, Cc) of {TRr}n (n=2–5) clusters. These oligomers are further enveloped by inner (Xi) as well as outer (Xa) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of {TR6} octahedra via common edges are more frequent than trimers and pentamers, in which the {TRr} clusters share common faces.

Metal Clusters. As They Were Born in Siberia

Key results of the researches in the field of cluster chemistry executed by scientists of Nikolaev Institute of Inorganic Chemistry (NIIC) of the Siberian Branch of Russian Academy of Sciences are presented. Structure and properties of some cluster compounds of niobium, tantalum, molybdenum, tungsten and rhenium for the first time synthesized in NIIC are briefly discussed. Some original results which are conceptually important in chemistry of metal cluster complexes are noted.

Change of magnetic and electronic features through subtle substitution in cubic, non-centrosymmetric extended rare-earth metal cluster complexes {TR3}X3

Abstract The new compound {IrCe3}I3 was synthesized by comproportionation reactions of stoichiometric ratios of CeI3, Ce and Ir. Single crystal X-ray diffraction structure determination shows that {IrCe3}I3 crystallizes with the cubic variant of the {TR3}X3 family (I4132, Z=8, a=12.450(1) A, V=1930.0(3) A3) and is isostructural with the recently reported {RuLa3}Br3. Octahedral {IrCe6} clusters share three common edges forming interpenetrating chains that run along the 41 screw axes. Magnetic measurements on pure powder samples of {IrCe3}I3 show paramagnetic behavior and, at temperatures below 2 K, a mictomagnetic state. The isostructural {RuLa3}Br3 is a Pauli paramagnet suggesting metallic conductivity which is consistent with band structure calculations where the Fermi level is placed below a pseudogap. For {IrCe3}I3, on the contrary, the Fermi level falls in a narrow gap rather than a pseudogap suggesting activated conductivity.

Synthesis, structural and magnetic characterisation of iron(ii/iii), cobalt(ii) and copper(ii) cluster complexes of the polytopic ligand: N-(2-pyridyl)-3-carboxypropanamide

Herein we describe the synthesis, structural and magnetic characterisation of three transition metal cluster complexes that feature the polytopic ligand N-(2-pyridyl)-3-carboxypropanamide (H2L): [Fe3(III)Fe2(II)(HL)6(O)(H2O)3][ClO4]5·3MeCN·4H2O, 1, [Co8(HL)8(O)(OH)4(MeOH)3(H2O)]-[ClO4]3·5MeOH·2H2O, 2, and [Cu6(L(ox))4(MeOH)(H2O)3]·MeOH, 3. Complex 1 is a mixed valence penta-nuclear iron cluster containing the archetypal {Fe3(III)O} triangular basic carboxylate cluster at its core, with two Fe(II) ions above and below the core coordinated to three bidentate pyridyl-amide groups. The structure of the octanuclear Co(II) complex, 2, is based upon a central Co4 square with the remaining four Co(II) centres at the 'wing-tips' of the complex. The cluster core is replete with bridging oxide, hydroxide and carboxylate groups. Cluster 3 contains an oxidised derivative of the ligand, L(ox), generated in situ through hydroxylation of an α-carbon atom. This hexanuclear cluster has a 'barrel-like' core and contains Cu(II) ions in both square planar and square-based pyramidal geometries. Bridging between Cu(II) centres is furnished by alkoxide and carboxylate groups. Magnetic studies on 1-3 reveals dominant antiferro-magnetic interactions for 1 and 2, leading to small non-zero spin ground states, while 3 shows ferro-magnetic exchange between the Cu(II) centres to give an S = 3 spin ground state.