Synthesis and characterization of heterometallic Rh/Ru complexes supported by 1,2-dichalcogenolato-o-carborane ligands

The 16-electron half-sandwich complexes Cp^∗Rh[E₂C₂(B₁₀H₁₀)] (E = S, 1a; Se, 1b) react with [Ru(COD)Cl₂]_x under different conditions to give different types of heterometallic complexes. When the reactions were carried out in THF for 24 h, the binuclear Rh/Ru complexes [Cp^∗Rh(μ-Cl)₂(COD)Ru][E₂C₂(B₁₀H₁₀)] (E = S, 2a; Se, 2b) bridged by two Cl atoms and the binuclear Rh/Rh complexes (Cp^∗Rh)₂[E₂C₂(B₁₀H₁₀)] (E = S, 3a; Se, 3b) with direct Rh-Rh bond can be isolated in moderate yields. [Ru(COD)Cl₂] fragments in 2a and 2b have inserted into the Rh-E bond. If the [Ru(COD)Cl₂]_x was reacted with 1a in the presence of K₂CO₃ in methanol solution, the product [Cp^∗Rh(COD)]Ru[S₂C₂(B₁₀H₁₀]] (4a), K[(μ-Cl)(μ-OCH₃)Ru(COD)]₄ (5a) and 3a were obtained. The B(3)-H activation in complex 4a was found. However, when the reaction between 1b and [Ru(COD)Cl₂]_x was carried out in excessive NaHCO₃, the carborane cage opened products {Cp^∗Rh[S₂C₂(B₉H₁₀)]}Ru(COD) (6b), {Cp^∗Rh[S₂C₂(B₉H₉)]}Ru(COD)(OCH₃) (7b) and 3b were obtained. All complexes were fully characterized by their IR, ¹H NMR and elemental analyses. The molecular structures of 2a, 2b, 3b, 4a, 5a, and 7b have been determined by X-ray crystallography.     

Synthesis,Characterization and Thermal Behavior of Two 4d‐4f Coordination Polymers Based on N and O Donor Ligands

Two new 4d‐4f coordination polymers, [Ag₂Nd(nic)₄(H₂O)₄·(ClO₄)·H₂O] ( 1 ) and [Ag₈Yb₄(inic)₈(ox)₆]· [Ag₂(inic)₂] ( 2 ) [nic = nicotinate, inic = isonicotinate and ox = oxalate] have been synthesized and characterized by element analysis, IR spectroscopy and thermal analysis, as well as single crystal X‐ray diffraction. Complex 1 exhibits a wavelike layer that is assembled from neodymium‐carboxylate subunits, silver centres and perchlorate ions. Complex 2 represents a extended heterometallic sandwich‐like layered network that is constructed from ytterbium‐oxalate layers and Ag(inic) chains.     

Syntheses,Structures, Luminescence,and Gas Adsorption Properties of Two New Heterometallic Complexes Involving Alkaline Earth Metals (Ca,Ba)

Two new 3D heterometallic frameworks, [Me₂NH₂][CaCd₂(BTC)(HBTC)₂] · 4H₂O ( 1 ) and [Ba₁₁Co₂(BTC)₈(μ₃‐OH)₂(μ₂‐H₂O)₆(H₂O)₁₆] ( 2 ) (H₃BTC = 1,3,5‐benzenetricarboxylic acid, Me₂NH₂ = protonated dimethylamine), were synthesized using solvothermal and hydrothermal techniques, respectively. Complex 1 features a 3D microporous framework; it contains hourglass‐like trinuclear [CaCd₂(COO)₆] clusters that are bridged by –COO^– groups and form zigzag chains. These chains are further interlinked by the –COO^– groups of BTC^3– ligands into 2D layers with interesting flower‐like configuration, which, in turn, are connected by HBTC^2– ligands to afford the 3D structure. Me₂NH₂⁺ cations not only balance the negative charges of the host framework but also play template roles to fill in the channels, further consolidating the whole framework. The complicated 3D network of complex 2 is constructed by the interconnection of 2D layers, which, in turn, are made of the infinite inorganic chains based on hexanuclear [Ba₆] clusters, and these 1D chains are decorated by {CoO₆} octahedrons. Interestingly, the 2D layer can be viewed as a unique structure composed of two different kinds of heart‐shaped rings, which partially overlapped in apical positions to produce a ten‐membered ring window. Moreover, the luminescence properties of 1 – 2 and the gas adsorption property of 1 have also been studied.     

A hexanuclear discrete assembly and a two dimensional coordination polymer constructed from heterotrinuclear [(CuL)2Zn]2+ nodes and dicyanamide spacer (H2L = salen type Schiff base ligands)

Two new Cu(II)–Zn(II) complexes as a discrete hexanuclear cluster [{(CuL¹)₂Zn}₂(μ_1,5-N(CN)₂)₂](ClO₄)₂ (1) and a two dimensional (2D) coordination polymer [(CuL²)₂Zn(μ_1,5-N(CN)₂)₂]_n (2) have been isolated by mixing two similar tetradentate Schiff bases H₂L¹ (N,N′-bis(ɑ-ethylsalicylidene)-1,3-propanediamine) and H₂L² (N,N′-bis(salicylidene)-1,3-pentanediamine) separately with Cu(ClO₄)₂·6H₂O, Zn(ClO₄)₂·6H₂O and NaN(CN)₂ ?at same reaction condition. The heterometallic complexes have been structurally characterized by single crystal X-ray analyses showing that both are formed by angular trinuclear nodes and μ_1,5-dicyanamide spacers. The trinuclear nodes ([(CuL¹)₂Zn]²⁺ in 1 and [(CuL²)₂Zn]²⁺ in 2 are produced in situ from their corresponding reactants. The two Schiff base ligands coordinating the Cu(II) ions through the N₂O₂ donor set are additionally bonded to a Zn(II) ion with the four phenoxido oxygen atoms that act as bridging atoms. The zinc ion completes its coordination geometry with two terminal nitrogen atoms of two different dicyanamide spacers. The orientation of spacers from zinc ion are convergent in 1 whereas divergent in 2. Thus, two [(CuL¹)₂Zn]²⁺ nodes are interconnected by double μ_1,5-dicyanamide bridges via Zn(II) centres to form discrete hexanuclear assembly of complex 1. On the other hand, [(CuL²)₂Zn]²⁺ nodes in 2 are joined by μ_l,5-dicyanamide that bridge Zn(II) to Cu(II) centres of symmetry related units in order to construct a 2D coordination polymer. Consequently, the final coordination environment around Zn(II) is octahedral in both complexes whereas that around Cu(II) are square planar and square pyramidal in 1 and 2 respectively.     

Reactivity of the heteronuclear cluster RuOs3(μ-H)2(CO)13 with indene

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (1) reacts with indene under thermal activation to afford the novel clusters RuOs₃(μ-H)(CO)₉(μ-CO)₂(η⁵-C₉H₇) (3), RuOs₃(μ-H)(CO)₉(μ₃,η⁵:η²:η²-C₉H₇) (4) and Ru₂Os₃(μ-H)(CO)₁₁(μ₃,η⁵:η²:η²-C₉H₇) (5), the latter two possessing indenyl ligands in the μ₃,η⁵:η²:η² bonding mode. Cluster 5 exists as a mixture of two isomers. The inter-relationship among the clusters has also been investigated.     

Chemistry of vinylidene complexes. XVI. Crystal and molecular structure of the novel tetranuclear μ2-μ3-bis-vinylidene complex (η-dppe)PdMn(μ3-CCHPh)PdMn(μ-CCHPh)(CO)4Cp2

The crystal and molecular structure of the novel tetranuclear complex (η²-dppe)PdMn(μ₃-CCHPh)PdMn(μ-CCHPh)(CO)₄Cp₂ (5) has been investigated. The metal core of 5 is a bent chain Pd(2)-Mn(2)-Pd(1)-Mn(1). The bond distances and angles are Mn(1)-Pd(1) 2.6025(6), Pd(1)-Mn(2) 2.8913(5), Mn(2)-Pd(2) 2.6463(4) Å, Mn(1)-Pd(1)-Mn(2) 140.2(2)°, Pd(1)-Mn(2)-Pd(2) 69.6(1)°. Complex contains two bridging vinylidene ligands coordinated to metal atoms in different ways. The CC bond lengths are 1.347(4) and 1.372(4) Å in the μ₂(η¹,η¹)-CCHPh and μ₃(η¹,η¹,η²)-CCHPh ligands, respectively. The η²-dppe ligand is coordinated to the Pd(2) atom to form the chelate cycle. Each of Mn(1) and Mn(2) atoms is bonded with the η⁵-C₅H₅ ring and two CO groups.     

Synthesis and electrocatalytic reactivity for water oxidation of two cerium complexes

Two cerium complexes with and without manganese ion, [MnCe₄(dipic)₆(H₂O)₂₀][Ce(dipic)₃]₂·7H₂O (dipic = dipicolinate) (1) and [Ce₂(H₂O)₄(O₂CMe)₆][Ce(H₂O)₄(NO₃)₂(O₂CMe)]₂·2H₂O·2MeOH (2), have been prepared, and their electrocatalytic reactivity for water oxidation has been investigated. Compound 1 is a heterometallic 3d-4f compound which possesses four Ce(IV) ions, two Ce(III) ions, and one Mn(II). Compound 2 is composed of three neutral parts, one of which is a dinuclear cerium molecule lying on an inversion center, and the other two are symmetric monomer units; the four cerium ions in 2 are all Ce(III). Electrochemical studies of 1 and 2 show that 1 can catalyze water oxidation at the potential ~1.5 V with an overpotential of ca. 900 mV versus NHE. Control potential electrolysis (CPE) experiments at 1.50 V of 1 displayed a stable current density of 2.5 mA/cm², and the calculated Faradaic efficiency is 60%. However, no electrocatalytic reactivity was observed for 2. By comparison experiments, it was found that the electrocatalysis of 1 may result from the cooperative catalytic effect of the 4f cerium ion and 3d transition metal manganese ion.     

Two 3d‐4f Heterometallic Coordination Polymers of Macrocyclic Oxamide with Benzotriazole‐5‐carboxylate Co‐ligand: Syntheses,Crystal Structures and Magnetic Properties

Two heterometallic 3d–4f coordination polymers, [Gd(CuL)₂(Hbtca)(btca)(H₂O)] · 2H₂O ( 1 ) and [Er(CuL)₂(Hbtca)(btca)(H₂O)] · H₂O · CH₃OH ( 2 ) (CuL, H₂L = 2,3‐dioxo‐5,6,14,15‐dibenzo‐1,4,8,12‐tetraazacyclo‐pentadeca‐7,13‐dien; H₂btca = benzotriazole‐5‐carboxylic acid) were synthesized by solvothermal methods and characterized by single‐crystal X‐ray diffraction. Complexes 1 and 2 exhibit a double‐strand meso‐helical chain structures formed by [Ln^IIICu^II₂] (Ln^III = Gd, Er) units by oxamide and benzotriazole‐5‐carboxylate bridges. They are isomorphic except that one free water molecule of 1 is replaced by a methanol molecule. All 1D chains are further interlinked by hydrogen bonds resulting in a 3D supramolecular architecture. The magnetic properties of the compound 1 and 2 are also discussed.     

Der Dihydridoiridium(III)‐Komplex [IrH2Cl(PiPr3)2] als Molekülbaustein für unsymmetrische Rhodium–Iridiumund Iridium–Iridium‐Zweikernverbindungen

The Dihydridoiridium(III) Complex [IrH₂Cl(P i Pr₃)₂] as a Molecular Building Block for Unsymmetrical Binuclear Rhodium–Iridium and Iridium–Iridium Compounds The title compound [IrH₂Cl(PiPr₃)₂] ( 3 ) reacts with the chloro‐bridged dimers [RhCl(PiPr₃)₂]₂ ( 1 ) and [IrCl(C₈H₁₄)(PiPr₃)]₂ ( 5 ) by cleavage of the Cl‐bridges to give the unsymmetrical binuclear complexes 4 and 6 with Rh(μ‐Cl)₂Ir and Ir(μ‐Cl)₂Ir as the central building block. The reactions of 3 with the bis(cyclooctene) and (1,5‐cyclooctadiene) compounds [MCl(C₈H₁₄)₂]₂ ( 7 , 8 ) and [MCl(η⁴‐C₈H₁₂)]₂ ( 9 , 10 ) (M = Rh, Ir) occur analogously and afford the rhodium(I)‐iridium(III) and iridium(I)‐iridium(III) complexes 11 – 14 in 70–80% yield. Treatment of [(η⁴‐C₈H₁₂)M(μ‐Cl)₂IrH₂(PiPr₃)₂] ( 13 , 14 ) with phenylacetylene leads to the formation of the substitution products [(η⁴‐C₈H₁₂)M(μ‐Cl)₂IrH(C≡CPh)(PiPr₃)₂] ( 15 , 16 ) without changing the central molecular core. Similarly, the compound [(η⁴‐C₈H₁₂)Rh(μ‐Br)₂IrH(C≡CPh)(PiPr₃)₂] ( 18 ) has been prepared; it was characterized by X‐ray crystallography.