Structural and solution studies of a novel tetranuclear silver(I) cluster of [1,3-di(2-methoxy)benzene]triazene

The synthesis, characterization, crystal structure, ¹H NMR, spectrophotometric and conductometric studies of a new tetranuclear silver(I) complex of [1,3-di(2-methoxy)benzene]triazene are reported. Reaction of the ligand with silver acetate resulted in the formation of a tetranuclear cluster with a four-member Ag-Ag ring core, composed of four triazenide ligands and four metals. The results of studies of the stoichiometry and formation and of complex in tetrahydrofuran solution were found to be in support of its solid state structure.     

Tetranuclear manganese(III) clusters containing both carboxylate and phosphonate bridging ligands

This paper reports two tetranuclear manganese clusters, namely, [Mn₄O₂(O₂CCH₃)₄(O₃PC₆H₁₁)₂(phen)₂] (1) and [Mn₄O₂(O₂CPh)₄ (O₃PC₆H₁₁)₂(bpy)₂] (2). Both contain a butterfly-like [Mn₄(μ₃-O)₂]⁸⁺ core. The neighboring Mn atoms within the core are bridged by the carboxylate groups, forming approximately a plane. The phosphonate ligands locate above and below the plane, and cap on top of the Mn₃O triangles by using its three phosphonate oxygen atoms. The magnetic measurements of complexes 1 and 2 reveal that dominant antiferromagnetic interactions are propagated between the magnetic centers.     

Crystal structures and magnetic properties of tetranuclear copper(II) complexes of N-(2-hydroxymethylphenyl)salicylideneimine with a defective double-cubane core

Tetranuclear Cu(II) complexes of N-(2-hydroxymethylphenyl)salicylideneimine (H₂L1-H) and its homologues (5-CH₃: H₂L1-Me, 5-Cl: H₂L1-Cl), [Cu(L1-H)]₄ · 3H₂O (1), [Cu(L1-Me)]₄ · 2CH₂Cl₂ (2), and [Cu(L1-Cl)]₄ · 2CH₂Cl₂ (3), have been characterized by X-ray crystal structure analyses and magnetic measurements. The structure analyses revealed that the complexes 1-3 have a defective double-cubane tetra copper(II) core connected by μ₃-alkoxo bridges. The intramolecular Cu?Cu distances are in the range from 5.251(2)-5.256(3) Å for the longest to 3.0518(9)-3.092(2) Å for the shortest. Each Cu(II) ion has a square-pyramidal geometry and the dihedral angles between adjacent Cu(II) basal planes are almost right angles. Magnetic measurements of the present complexes indicate that weak antiferromagnetic interactions (J=−15 to −19 cm⁻¹) between neighboring copper(II) ions are dominant in these tetracopper cores.     

Benzene-1,2-dithiolate-induced assembly of reactive iridium fragments into tetranuclear octahydride complexes

The tetrametallic compound [Ir₄(μ-1,2-S₂C₆H₄)₂(μ-H)₂H₆(PⁱPr₃)₄(NCMe)] (1) has been obtained by treatment of the reactive cationic complex [IrH₂(PⁱPr₃)(NCMe)₃]BF₄ with the benzene-1,2-dithiolate anion. In the solid state, this tetrametallic compound exhibits an irregular nearly planar metal skeleton with the two dithiolate anions bridging the four metal centres from the same side of the tetrametallic plane. Even though all iridium atoms coordinate one PⁱPr₃ ligand, two bridging S atoms and, at least, two hydrides, they show different electronic and coordination environments. This unusual structure is maintained in solution, even after substitution of the labile acetonitrile ligand by other Lewis bases such as ethylene or carbon monoxide.     

Influence of substituents on the structures of hybrid complexes constructed from tetranuclear copper(I) 1,2,4-triazolate clusters and octamolybdates

By changing the substituents on 1,2,4-triazole ring, six novel organic-inorganic hybrid complexes constructed from tetranuclear copper(I) 1,2,4-triazolate clusters and octamolybdates, [{Cu₄(L)_x}Mo₈O₂₆] (L = 3,5-diamino-1,2,4-triazole (datrz) and x = 4 for 1; L = 3-amino-1,2,4-triazole (3atrz) and x = 4 for 2; L = 3,5-dimethyl-1,2,4-triazole (dmtrz) and x = 4 for 3; L = 3,5-dimethyl-4-amino-1,2,4-triazole (dmatrz) and x = 6 for 4; L = 3,5-diethyl-4-amino-1,2,4-triazole (deatrz) and x = 4 for 5; L = 3,5-di(n-propyl)-4-amino-1,2,4-triazole (dpatrz) and x = 3 for 6), were obtained. The tetranuclear Cu(I) cluster in compound 1 acts as charge-compensating unit, which is the first polynuclear metal 1,2,4-triazole structure only with N1, N2 bridging mode. Compounds 2, 4, 5 and 6 are of polymeric 1D chains and 3 is of a 2D layer structure. In 2, three distinct Cu(I)-coordination geometries, distorted tetrahedral, T-shaped and V-shaped linear Cu(I), are observed in the same structure. The first extended hybrid structure constructed by δ-octamolybdates is founded in 4. A novel [Mo₈O₂₆]⁴⁻ anion is found in 5, which contains only three crystallographically independent Mo atoms. In compounds 5 and 6, terminal oxo groups of octamolybdate cluster act as μ₃-oxo bridges to link the copper(I) coordination complexes; such an unusual linking manner is unique in the coordination chemistry of octamolybdates with transition metal fragments. The influences of substituent on the structures of the tetranuclear units are also discussed in details.     

A tetracopper(II) complex with N,N′-bis(picolinoyl)hydrazine

Synthesis, physical properties and X-ray structure of a hydrated tetranuclear copper(II) complex [Cu₄(μ-diph)₂(μ-H₂O)₂(O₂CCH₃)₄(H₂O)₂]·4H₂O with N,N′-bis(picolinoyl)hydrazine (H₂diph) are reported. The centrosymmetric complex has two types of copper(II) centres with distorted square-pyramidal N₂O₃ coordination spheres. The dinucleating trans planar diph²⁻ ligands are parallel to each other and act as N₂O-donor to one metal centre and N₂-donor to the other metal centre. The complex has a rectangular {Cu₄(μ-N-N)₂(μ-OH₂)₂} core with Cu···Cu distances as 4.834(1) and 3.762(1) Å. Solid state as well as solution electronic spectra show several transitions in the wavelength range 700-280 nm. The room temperature (298 K) solid state magnetic moment is 3.55 μ_B. The powder EPR spectra at 298 and 130 K are very similar and axial (g_∥ = 2.25 and g_⊥ = 2.08) in character.     

Preparation and reactivity of a tetranuclear Fe(II) core in the metallothionein α-domain

Metallothioneins (MTs) are small cysteine-rich proteins which exhibit high affinities for various metal ions and play roles in storage of essential metals and detoxification of toxic metals. Studies on the redox properties of MTs have been quite limited. Recently, we focused on the α-domain of MT (MTα) as a protein matrix and incorporated a tetranuclear metal cluster as a reductant. UV-visible, CD and MS data indicate the formation of the stable tetranuclear metal-cysteine cluster in the MTα matrix with Fe^II₄-MTα and Co^II₄-MTα species existing in water. Furthermore, the Fe^II₄-MTα species was found to promote the reduction of met-myoglobin and azobenzene derivatives under mild conditions. Particularly, the stoichiometric reduction of methyl red with Fe^II₄-MTα (1:1) was found to proceed with a conversion of 98% over a period of 6 h at 25 °C. This indicates that all of the four Fe(II) cores contribute to the reduction. In this paper, we describe the preparation and reactivity of the tetranuclear iron cluster in the protein matrix.     

Exchange integral for a variety of tetranuclear ferredoxins

The temperature dependence of EPR spectra of oxidized [4Fe-4S1]^{(?1, ?2)} ferredoxins (previously designated HiPIP) and a reduced [4Fe-4S1]^(?2,?3) ferredoxin have been analyzed so as to determine the energy of a low-lying excited electronic state. The values obtained were: Center S-3 from beef heart, 44 cm^?1; Center S-3 from mung bean, 53 cm^?1; the [4Fe-4S1]^(?1,?2) ferredoxin from Thermus thermophilus, 78 cm^?1; Center N-2 of NADH ubiquinone reductase, 83 cm^?1. Increasing axial distortion in the EPR spectra of the [4Fe-4S1]^(?1,?2) ferredoxins was associated with higher energy differences. Center N-2, a [4Fe-4S1]^(?2,?3) iron-sulfur cluster does not fit this relationship.     

Synthesis, X-ray crystal structure and properties of a novel tetranuclear unsymmetrical (μ-SO4) copper(II) complex: relevance to SO2 fixation

The synthesis, by fixation of SO₂, the unusual crystal structure, and the spectral and redox properties of the new compound [Cu₄(TPPNOL)₂(μ-SO₄)₂](ClO₄)₂ (1) [HTPPNOL (N,N,N′-tris-(2-pyridylmethyl)-1,3-diaminopropan-2-ol)] are reported. In 1, the copper(II) ions are bridged by the alkoxo oxygen atoms of the HTPPNOL ligand and by exogenous sulfate bridges. The structure of 1 consists of a centro-symmetric tetranuclear core or a “Dimer of Dimers” complex, in which a μ-O,O′ sulfate oxygen atom is further coordinated to the copper centre of another similar dinuclear unit through a μ-O,O, sulfate bridge resulting in a tetranuclear arrangement. Thus, the dinuclear units are linked by two μ-O,O sulfate bridges. The simultaneous presence of two distinct coordination modes for the sulfate group in this structure is rare and 1 represents the first coordination compound presenting μ-O,O′ and μ-O,O type structures. The SO₂ fixation was monitored by changes in the electronic spectra which indicated the formation of the intermediate hydroxo complex [Cu₂(TPPNOL)(OH)₂]⁺, in basic medium, which, we propose, acts as the nucleophile in the SO₂ fixation mechanism.     

Anhydrous tetranuclear, dinuclear, and dimeric lanthanide complexes bearing tetradentate Schiff bases

This contribution describes the synthesis and complete characterization of dinuclear (Ln₂(SB)₃) and rigorously dimeric ([(SB)Ln(N(TMS)₂)]₂) lanthanide complexes bearing “saturated” tetradentate Schiff bases (SB). The molecular connectivities, nuclearity, and metal ion coordination geometries in these compounds are governed by the interplay of Schiff-base steric requirements, metal ion radius, and reaction conditions (i.e., solvent choice, concentration, and temperature); the impact of these factors will be discussed and emphasized in the context of structural similarities and notable intramolecular interactions within these related compounds. Also presented is a tetranuclear Nd³⁺ complex exhibiting a ladder arrangement of metal ions and μ-oxo bridges; its formation occurs by the destruction of THF at elevated temperatures. All the compounds presented can be reproducibly synthesized in high yields and analytical purity.