Synthesis and structure of [{As(NtBu)3}2Li6] containing an [As(NtBu)3]3− trianion

Attempts to prepare the [As(N^tBu)₃]³⁻ trianion by the reaction of As(NMe₂)₃ with [^tBuNHLi]_n (1:3 monomer equiv.) proved unsuccessful. However, if the reaction is carried out with an excess of ^tBuNH₂ (3 equiv.) the target complex [{As(N^tBu)₃}₂Li₆] (1) is obtained. This is the first example of a complex containing an [As(NR)₃]³⁻ trianion.     

Ten-vertex osmamonocarbaboranes via arachno and nido {CB9} monocarbaboranes. Polyhedral contraction promoted by [OsCl2(PPh3)3] in MeOH and the crystal and molecular structure of [1-H-1,1-(PPh3)2-2-Ph-3-(OMe)-isocloso-1,2-OsCB8H7]

Reactions of [OsCl₂(PPh₃)₃] 1 with the [NEt₄]⁺ salts of the [6-Ph-nido-6-CB₉H₁₁]⁻ anion 2 and the [arachno-6-CB₉H₁₄]⁻ anion 3 each proceed selectively in methanol solution with the elimination of one boron-containing fragment from the starting cluster polyhedron, yielding together a short series of three novel 10-vertex hydridoosmamonocarbaboranes of isocloso {OsCB₈} cluster geometry.     

Synthesis, structural characterization and third-order non-linear optical property of new three-dimensional metal-organic polymer [Fe2(μ10-btc)0.5(μ2-ox)0.5(μ2-O)1.5]n

One new metal-organic polymer formulated as [Fe₂(μ₁₀-btc)_0.5(μ₂-ox)_0.5(μ₂-O)_1.5]_n 1 (btc = 1,2,4,5-benzenetetracarboxylate, pyramellitate; ox = oxalate) has been synthesized by low-temperature solid-state reaction and characterized by single-crystal X-ray diffraction, elemental analyses, TGA, IR spectra and UV–visible spectra. Complex 1 presents the first 3D coordination network structure constructed by bridging btc, ox and O mixed ligands. In 1, carboxyl groups of btc are all deprotonated and they have a new type of μ₁₀-btc coordination mode. The third-order non-linear optical (NLO) properties of the title compound 1 were also investigated and they exhibit the reverse saturable absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 5.98 × 10⁻³⁰ esu for 1 in a 7.45 × 10⁻⁴ mol dm⁻³ DMF solution.     

Synthesis, structural characterization and ethylene polymerization behavior of complex [Ph4P][CrCl3{HB(pz)3}] [HB(pz)3 = hydrotris(1-pyrazolyl)borate]

Reaction of CrCl₃(THF)₃ with K[HB(pz)₃] in THF leads to the formation of the complex K[CrCl₃{HB(pz)₃}] (1). The salt metathesis of complex 1 with [Ph₄P]Br in CH₂Cl₂ yields the complex [Ph₄P][CrCl₃{HB(pz)₃}](2). The structure of complex 2 · CHCl₃ has been determined by single crystal X-ray diffraction. In the anion the metal centre shows a distorted octahedral geometry with the hydrotris(1-pyrazolyl)borate bonded as N,N′,N″-donor tripod ligand and three chloride atoms completing the co-ordination sphere. Complex 2 in the presence of MAO leads to the formation of an active catalyst for the polymerization of ethylene.     

Ferromagnetic coupling in a novel dicyanamide-bridged dinuclear gadolinium(III) complex [Gd2(dca)4(OH)2 (NITpPy)4] (NITpPy = 4-pyridyl-nitronyl nitroxide radical)

The novel six-coordinated gadolinium(III) complex of formula [Gd₂(dca)₄(OH)₂(NITpPy)₄] (1) (dca = dicyanamide, NITpPy = 4-pyridyl-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-oxy-3-oxide) has been prepared and characterized by X-ray crystallography. Compound 1 is a dimer structure made up of double μ_1,5-dca-bridged gadolinium(III) ions and one terminal dca ligand; variable-temperature magnetic susceptibility measurements reveal the occurrence of a significant ferromagnetic interaction directly spin polarization through the NITpPy–Gd(III)–NITpPy pathway with J = 11.56 cm⁻¹.     

The structural characterization and hydroformylation activity of the tri-rhodium complex [Rh3(μ2-dppm)2(μ2-CO)3(K-CO)3]BF4

Rh₂(cod)₂(μ₂-dppm)(μ₂-Cl)]BF₄ (1) rearranges under carbon monoxide to give [Rh₃(μ₂-dppm)₂(μ₂-CO)₃(K¹-CO)₃]BF₄ (2). Complex 2 has been structurally characterized by single crystal X-ray crystallography. The hydroformylation activities of 1 and 2 were compared for substrates styrene and 1-hexene and the activity of 2 found to be unexpectedly high.     

First X-ray structure of discrete anion [HgBr5]: Synthesis, characterization and single crystal X-ray structure determination of [Co(NH3)6][HgBr5]

A new cobalt(III) complex salt, [Co(NH₃)₆][HgBr₅](1) was crystallized from a solution of hexaamminecobalt(III)bromide and potassium tetrabromomercurate(II) in aqueous medium in 1:1 molar ratio. This complex salt has been characterized by elemental analyses, spectroscopic techniques (e.g. UV/Visible, IR), solubility product and conductance measurements. The complex salt crystallizes in Orthorhombic crystal system with space group Pnma. Single crystal X-ray structure determination revealed the presence of discrete ions: [Co(NH₃)₆]³⁺ cation and a new anion [HgBr₅]³⁻. This is the first structural report of a complex salt containing this new anion. The structure consists of stacks of cations and anions demonstrating supramolecular arrangements through N–HBr hydrogen-bond interactions. The crystal lattice is stabilized by these non-covalent interactions besides electrostatic interaction.     

Synthesis and molecular structure of the sodium arsanediyl zincate [(thf)Na]2[(EtZn)6(AsSiiPr3)4]

The reaction of NaAs(H)SiiPr₃ with ZnEt₂ in the presence of additional triisopropylsilylarsane yields the heterobimetallic complex [(thf)Na]₂ [(EtZn)₆(AsSiiPr₃)₄] (1) in the shape of red prisms. The Na–As and Zn–As bond lengths show values of 301/309 pm and between 247 and 260 pm, respectively.     

Diplatinum(III) [Cl2(μ2-amidinate)4] compound derived from air oxidation of mononuclear cis-[Pt(NH3)2(amidine-κ)2] complex

The dinuclear platinum(III) complex [Pt₂Cl₂{μ₂-N(H)C(Et)N(H)}₄] (2) has been prepared by heating cis-[Pt(NH₃)₂{NHC(NH₂)Et}₂](Cl)₂ (cis-1) under aeration conditions in an EtOH/H₂O mixture at 70 °C for 2 d and it was characterized by elemental analyses (C, H, N), ESI⁺-MS, IR, ¹H and ¹³C NMR spectroscopies and also by X-ray diffraction. Complex 2 represents the second Pt^III dimer stabilized by the amidinate ligand ever known and it has a lantern-type structure with four amidinate ligands bridging two Pt^III centers with Pt–Pt distance of 2.4809(2) Å.     

Synthesis, structure and photoluminescence of a novel palladium(I) compound: [Pd3(μ3-Cl)2(dppp)3][Pd2(μ2-Cl)3(PPh3)2](PPh3)2

Pd(PPh₃)₂Cl₂ reacts with PdCl₂ and 1,3-bis(diphenylphosphine)propane (dppp) in ethanol–DMF–pyridine mixed solvent to yield a novel palladium(I) compound [Pd₃(μ₃-Cl)₂(dppp)₃][Pd₂(μ₂-Cl)₃(PPh₃)₂](PPh₃)₂. It features an isolated structure based on [Pd₃(μ₃-Cl)₂(dppp)₃]⁺ cations having triangulo-palladium clusters and [Pd₂(μ₂-Cl)₃(PPh₃)₂]⁻ anions in which the coordination environment of palladium is an unusual tetrahedral geometry. Its photoluminescence is measured.     

Supramolecular π–π assembly of a neutral [Cu(salen)] complex via the templating effect of an ionic inorganic complex Na2[Cu(mnt)2] forming a framework type material having well-defined channels

A classical ionic inorganic complex Na₂[Cu(mnt)₂] (mnt²⁻ = maleonitriledithiolate = 1,2-dicyanoethylenedithiolate), that acts as a template in assembling neutral [Cu(salen)] (salen = bis(salicylidene)ethylenediamine) complexes forming a framework type arrangement, is accommodated in the channel formed in the crystal structure of a new type of host–guest compound [Cu(salen)]₄ · Na₂[Cu(mnt)₂] (1). The non-covalent supramolecular interactions among [Cu(salen)] complexes and between [Cu(salen)] and [Cu(mnt)₂]²⁻ complexes in the crystal lattice of 1 result in weak antiferromagnetic coupling.     

A new type of supramolecular assembly consisting of crown ether complex cation and a polyoxometalate anion: Synthesis and crystal structure of [Na(C20H24O6)(CH3CN)2]2[Mo6O19] · 4CH3CN

A novel supramolecular assembly consisting of sodium-dibenzo-18-crown-6(DB18C6) complex cation [Na(C₂₀H₂₄O₆)(CH₃CN)₂]²⁺ and isopolyanion [Mo₆O₁₉]²⁻ has been demonstrated in the 3D structure of [Na(C₂₀H₂₄O₆)(CH₃CN)₂]₂[Mo₆O₁₉] · 4CH₃CN (1). Weak intermolecular forces (C–HO hydrogen bonds) between isopolyanion and crown ether play a significant role in the construction of supramolecular framework in the crystal structure of 1. Compound 1 has been characterized in the solid state by single crystal X-ray diffraction, IR, CHN analysis, and TGA.     

A novel disubstituted Lindqvist-type polyoxomolybdate [Te2Mo4O19] supporting two organic vanadyl moieties: Synthesis, characterization, and crystal structure of {[V(2,2-bipy)2]2(4,4-bipy)[Te2Mo4O19]}

The first example of disubstituted Lindqvist-type polyoxomolybdate {[V(2,2-bipy)₂]₂(4,4-bipy)[Te₂Mo₄O₁₉]} has been synthesized hydrothermally and characterized by elemental analyses, XPS, IR, TG-DTA and X-ray single crystal diffraction. The structural analysis shows that the neutral molecular unit [V(2,2-bipy)₂]₂[Te₂Mo₄O₁₉] consists of a novel Lindqvist-type polyanion [Te₂Mo₄O₁₉]⁶⁻ supporting two vanadyl moieties [V(2,2-bipy)₂]³⁺, and such neutral molecules are joined together by π − π stacking interactions between the pyridine groups to form a two-dimensional grid-like network with non-coordinating “guest” 4,4-bipys encapsulated.     

Synthesis, crystal structure and NMR of [Na(DB18C6)(CH3CN)]3[α-AsM12O40] (M = Mo/W)

Two super-molecular complexes [Na(DB18C6)(CH₃CN)]₃[α-AsM₁₂O₄₀] (M = Mo/W) were obtained by solvothermal reaction and characterized by IR,¹H ¹³C and gUMBC NMR, X-ray. The result reveals that the complex consists of a [α-AsM₁₂O₄₀]³⁻ (M = Mo/W) anion with α-Keggin structure, and three complex [Na (DB18C6)(CH₃CN)]⁺ cations in which every sodium ion is located in the cavity of dibenzo-18-crown-6 with 6 Na–O bonds and coordinated with one of the terminal O atom of [α-AsM₁₂O₄₀]³⁻ (M = Mo/W) and the N atom of CH₃CN from two sides of the distorted DB18C6 plane, respectively. The three terminal O atoms linked with sodium ion are from a single M₃O₁₃ (M = Mo/W) triplet of the α-Keggin metalatoarsenate anion, and M–O_b (M = Mo/W) bonds exhibit alternating single–double bond character.     

Synthesis, characterization and crystal structure of cis,mer-[ReH(CO)2{PPh(OMe)2}3]

The dicarbonylhydride complex cis,mer-[ReH(CO)₂{PPh(OMe)₂}₃] (1) was serendipitously obtained when, in an attempt to replace a CO ligand by the phosphonite ligand PPh(OMe)₂ in [ReH(CO)₃(L)] (L = PPh₂OCH₂CH₂OPPh₂), this complex was treated with PPh(OMe)₂ under UV irradiation. The complex 1 was characterized by IR, ¹H and ³¹P{¹H} NMR spectroscopy and by crystal structure determination. The spectroscopic features are consequent with the cis,mer configuration showed by the X-ray crystallographic analysis of the complex. The environment of the metal centre is a distorted octahedron.     

Synthesis and structural characterization of an alternating double aquo-bridged and single cyano-bridged polymeric barium–iron complex: {[Ba2(phen)4(H2O)6Fe(CN)6]·Cl·2(phen)·3H2O}n

A new alternating double aquo-bridged and single cyano-bridged polymeric complex {[Ba₂(phen)₄(H₂O)₆Fe(CN)₆]·Cl·2(phen)·3H₂O}_n (1) (phen = 1,10-phenanthroline) has been synthesized and structurally characterized. In the crystal structure the two centrosymmetric [Ba₂(phen)₄(H₂O)₆] units are bridged through two trans CN groups of [Fe(CN)₆]³⁻ ion, which results in the formation of a zig-zag polymeric chain. In each [Ba₂(phen)₄(H₂O)₆] unit, the two Ba centers are joined by double aquo bridges. Both the Ba atoms are 9-coordinated with distorted mono-capped square antiprismatic geometry. An elaborate hydrogen bonding system holds the parallel polymeric chains together.     

Self-assembled chloro-bridged metallo-prismatic cations of the general formula [M6(η-C5Me5)6(μ3-tpt)2(μ-Cl)6] (M = Rh, Ir; tpt = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine)

Two cationic pentamethylcyclopentadienyl metal-based hexanuclear complexes with trigonal prismatic architecture have been synthesised through a two-step strategy. The dinuclear complexes [M(η⁵- C₅Me₅)(μ-Cl)Cl]₂ (M = rhodium and iridium) react with 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (tpt) in dichloromethane to give the trinuclear complexes [Rh₃(η⁵-C₅Me₅)₃(μ₃-tpt)Cl₆] (1) and [Ir₃(η⁵-C₅Me₅)₃(μ₃-tpt)Cl₆] (2), respectively. Addition of silver triflate to 1 and 2 in dichloromethane connects two identical triangular panels to form the hexanuclear metallo-prismatic cations [Rh₆(η⁵-C₅Me₅)₆(μ₃-tpt)₂(μ-Cl)₆]⁶⁺ (3) and [Ir₆(η⁵-C₅Me₅)₆(μ₃-tpt)₂(μ-Cl)₆]⁶⁺ (4), respectively. Cations 3 and 4 have been isolated as their triflate salts and characterised by ¹H NMR, IR and UV/visible spectroscopy.     

Ferromagnetic mixed tribridged dinuclear copper(II) complex [Cu2(OAc)2(OH)(dpa)2]PF6 · H2O (dpa = 2,2′-dipyridylamine): 3D superstructure based on hydrogen bond and π…π interaction

A new dinuclear complex [Cu₂(OAc)₂(OH)(dpa)₂] PF₆ · H₂O (1) is prepared and structurally and magneto-structurally characterized. The monocationic core contains one acetate in familiar bidentate η¹:η¹:μ₂-bridge and another in the rare monoatomic bridge along with one hydroxo intermediary. 1 packs through N–H…O and O–H…O hydrogen bonds and π…π interaction resulting a 3D supramolecular continuum and displays high-energy intraligand ¹(π − π^*) fluorescence and intraligand ³(π − π^*) phosphorescence in glassy solution.     

Organically templated Np(IV) coordination polymer with in situ formed oxalate anion (ImidazoleH)[Np(C2O4)(CH3SO3)3(H2O)2]

The reaction of Np(V) methanesulfonate solution with imidazole led to the in situ formation of oxalic acid and the reduction of Np(V) to Np(IV). As a result, the novel organically templated organic polymer, (ImidazoleH)[Np(C₂O₄)(CH₃SO₃)₃(H₂O)₂], was formed. The structure consists of infinite chains of [Np(C₂O₄)(CH₃SO₃)₃(H₂O)₂]⁻ and imidazolium cations. The crystal structure is confirmed by IR and UV–vis spectroscopic data. This complex is the first example of structurally characterized 1:1 An(IV) oxalate.     

Hexanuclear 4d–4f complexes [Ln2Ag4(ina)8(H2O)10][NO3]2 · 4H2O (Ln = Sm, Eu, Dy): Syntheses, structures and photoluminescent properties

Hexanuclear 4d–4f heterometallic complexes, [Ln₂Ag₄(ina)₈(H₂O)₁₀][NO₃] ₂ · 4H₂O [Ln = Sm (1), Eu (2), Dy (3) and Hina = isonicotinic acid], have been synthesized by the hydrothermal reaction of lanthanide oxides, Ag^I, and isonicotinic acid at a suitable temperature. Single-crystal X-ray diffraction studies indicate that these 4d–4f complexes consist of extended 1D zigzag chains structure built upon [Sm₂Ag₄(ina)₈(H₂O)₁₀] subunits connected by Ag–Ag interactions. Furthermore, the photoluminescent properties of the complex 2 were studied.