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.     

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.     

Modern aspects on tri- and tetranuclear cluster complexes supported by phosphido bridges

This report on small cluster complexes with metal-metal bonds in the field of coordination chemistry documents results in the following scientific areas. (1) Systematic synthetic routes via ditransition metal carbonyl derivative of manganese and rhenium (group 7) to functionalizedtriangulo- andtetrahedro-clusters including structural characterization, (2) Dynamic properties of mono- and diauration isomers like M₂(μ-AuPR₃)(μ-PCyH)(CO)₈/M₂(μ-H)(μ₃-PCy(AuPR₃))(CO)₈ (isomerization) and M₂(μ-AuPR₃)₂(μ₄-PCy)(CO)₈/M₂(μ-AuPR₃)(μ₃-PCy(AuPR₃))(CO)₈ (M = Mn, Re; R = organic residue) (rearrangement and valence isomerization) and MM’(μ-H)(μ-PCy₂)(μ₄-PCy(AuPR₃))(CO)₆ (M = M’, M ≠ M’) (topomerization) going from one to the other homologue and the kinetic study of isomerization in the framework Re₂(AuPCy₃)₂(μ-PMeN₂(μ-C(Bu)O)(CO)₆, (3) Correlations of chirality transfer in diastereomerictetrahedro-clusters Re₂(M¹PR₃)₂(μ-PCy₂)(CO)₇(η¹-L*) (M¹ = coin metals, L* = chiral ligand as (+) or (-) prolinate, for example) from CD data. These selected contributions will be discussed to answer the question “Do small cluster complexes remain as a future challenge in cluster chemistry?”     

Monometallic and heterobimetallic complexes derived from salen-type ligands

Mononuclear and heterodinuclear complexes of the salen-type ligand H₂LH₂ [H₂LH₂ = 2,2′-[1,2-dihydroxybenzene-4,5-diylbis(nitrilomethylidine)]bis(3,5-di-tert-butylphenol)] were prepared, whereof [{Mn(CH₃OH)₂}LH₂]Cl, [ML()] (M = Ni, Cu, CrCl(py); py = pyridine, Cp^∗ = pentamethylcyclopentadienyl) were characterized by X-ray analysis. Additionally, cyclic voltammetric investigations were performed to ascertain the influence of the second transition metal complex fragment []²⁺ on the metallo salen ligand. Moreover, the complexes were tested in the catalytic epoxidation of styrene. Although the complexes are quite sensitive towards oxidants, monometallic complex [{Mn(CH₃OH)₂}LH₂]Cl exhibited a conversion of 70.6% with styrene oxide selectivity of 88% over 1 h at room temperature.     

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.     

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,Magnetism, and Thermostability of a Series of Two‐Dimensional Lanthanide–Nickel Heterometallic Coordination Polymers

A series of Ln–Ni heterometallic coordination polymers, {[Ln₂Ni(MIDA)₄(H₂O)₆](H₂O)₄} (Ln = La ( 1 ), Ce ( 2 ), Pr ( 3 ), and Nd ( 4 ); H₂MIDA = N‐methyl‐iminodiacetic acid), were obtained under hydrothermal conditions. Single crystal X‐ray diffraction revealed that they feature two‐dimensional isomorphic frameworks, which could be viewed as the construction by one‐dimensional {Ln}_n chain connecting by bridges of [Ni(MIDA)₂]². The magnetic measurements reveal that compounds 2 – 4 exhibit antiferromagnetic properties. TGA results indicate compounds 1 and 4 have good thermostability with the critical temperature of 375 °C.     

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.     

Heterobimetallic platinum–copper and platinum–silver transition metal complexes based on cis-[Pt](CCPh)2: an overview

The reaction of cis-[Pt](CCPh)₂ {[Pt]=(bipy)Pt, (bipy′)Pt; BIPY=2,2′-bipyridine, bipy′=4,4′-dimethyl-2,2′-bipyridine} with different copper(I) and silver(I) salts [M′X] (M′=Cu, Ag; X=inorganic or organic ligand) produces alkynyl-bridged (hetero)bi-, tri-, tetra- or pentametallic transition metal complexes. The structural aspects and reaction chemistry of such species and the preference for one coordination mode over another is discussed. The interconversion and mechanistical aspects in the formation of the latter complexes is also reported.     

Synthesis,Structure and Luminescence of Cd3Cu2 and Cd2Ni4 Heteronuclear Complexes with Macrocyclic Oxamide and 5‐Sulfosalicylicate

Two novel heteronuclear complexes [Cd₃(SSAL)₂(CuL)₂(H₂O)₄]_n ( 1 ) and [Cd₂(HSSAL)₂(NiL)₄] · 4H₂O ( 2 ) were synthesized and structurally determined, where SSAL is the fully deprotonated 5‐sulfosalicylic ion (CuL and NiL, H₂L = 2,3‐dioxo‐5,6,14,15‐dibenzo‐1,4,8,12‐tetraazacyclopentadeca‐7,13‐diene). Compound 1 displays a 1D ladder‐like chain and all these chains are further interlinked through hydrogen bonds resulting in a 2D architecture. The structure of 2 consists of 5‐sulfosalicylates and an oxamido‐bridge and is arranged in butterfly‐like hexanuclear molecules. The luminescent properties of compounds 1 and 2 are also discussed.