Photochemical [2+2] cycloaddition of the olefinic double bonds in the supramolecular rectangle [Ru4(η6-p-cymene)4(μ-oxalato)2(μ-4,4′-bipyridylethylene)2]4+

Self-assembly of 4,4′-bipyridylethylene (bpe) bidentate connector with the dinuclear arene ruthenium clip [Ru₂(η⁶-p-cymene)₂(μ-oxalato)Cl₂] in the presence of silver triflate affords the cationic organometallic rectangle [Ru₄(η⁶-p-cymene)₄(μ-oxalato)₂(μ-bpe)₂]⁴⁺ ([1][CF₃SO₃]₄). Upon UV irradiation of a methanol solution of [1]⁴⁺, dimerisation of the olefinic double bonds of the two parallel bpe ligands occurs, thus giving rise to the [2+2] cycloaddition derivative [Ru₄(η⁶-p-cymene)₄(μ-oxalato)₂(μ-tpcb)]⁴⁺ ([2][CF₃SO₃]₄) (tpcb = tetrakis(4-pyridyl)cyclobutane). The [2+2] photodimerisation reaction was followed by ¹H NMR spectroscopy. Moreover, the molecular structure of these two systems was deduced by one-dimensional and two-dimensional NMR experiments (¹H, ¹³C, ROESY, COSY, HSQC). These data suggest the formation of only the rctt-tetrakis(4-pyridyl)cyclobutane isomer.     

Molecular structure of [In2(μ,η1-OR)(μ,η2-OR)(η2-OR)3(η1-OR)] R = C2H4NMe2, a pincer ligand

Functional indium [In(OR)₃]_m alkoxides (R = C₂H₄OMe, C₂H₄NMe₂) have been obtained by alcoholysis of In[N(SiMe₃)₂]₃ and characterised by elemental analysis, FT-IR and NMR spectroscopy. The 2-dimethylaminoethoxide was characterised by X-ray diffraction. It corresponds to the association of two InO₆ octahedra giving the unsymmetrical dimer [In₂(μ,η¹-OR)(μ,η²-OR)(η²-OR)₃(η¹-OR)] (2). 2 was used as a pincer ligand toward Cu(acac)₂.     

Models of intermediates in metallocene-catalyzed alkene polymerizations: observation of a d0 cationic titanium–alkyl-alkene complex and decomposition by β-allyl elimination

Low temperature activation of Cp^*₂Ti[η¹,η¹- CH₂CH(CH₂CHCH₂)CH₂] (3) with [HN(CH₃)(C₆H₅)₂] [B(C₆F₅)₄] led to the formation of Cp^*₂Ti[η¹,η²-CH₂CH(CH₃)CH₂CHCH₂][B(C₆F₅)₄] (6) as determined by ¹H NMR spectroscopy. Cp^*₂Ti[η¹,η²-CH₂CH(CH₃)CH₂CHCH₂][B(C₆F₅)₄] undergoes rapid quantitative β-allyl elimination at temperatures as low as −140 °C. The resulting cationic titanium allyl complex [Cp^*₂Ti(η³-CH₂CHCH₂)][B(C₆F₅)₄] (4) exhibits a static structure at low temperatures, but interconversion of η³–η¹ binding modes can be observed at higher temperatures. Lineshape analysis of this process yielded ΔG³(−10 °C)= 13.7 ± 0.6 kcal mol⁻¹, ΔH³=9.8 ± 0.6 kcal mol⁻¹, and ΔS³=−15 ± 3 eu. The use of neutral borane B(C₆F₅)₃ also resulted in β-allyl elimination with the formation of [Cp^*₂Ti(η³-CH₂CHCH₂)][CH₂=CHCH₂B(C₆F₅)₃] (8).     

Semi-rigid N-para-ferrocenyl(benzoyl)amino-acid esters for biomaterials: synthesis and characterization of Fc-C6H4CONHCH(R)CO2Me where Fc = (η5-C5H5)Fe(η5-C5H4) and R=H,CH3,CH2CH(CH3)2,CH2C6H5 and the X-ray crystal structures of Fc-C6H4CO2Me and the l-alanine derivative Fc-C6H4CONHCH(CH3)CO2Me

A series of N-para-(ferrocenyl)benzoyl amino-acid esters, para-Fc(C₆H₄)CONHCH(R)CO₂CH₃ {Fc = (η⁵-C₅H₅)Fe(η⁵-C₅H₄); R = H, CH₃, CH₂CH(CH₃)₂, CH₂C₆H₅}, 3–6 have been prepared by coupling para-(ferrocenyl)benzoic acid to the amino-acid esters (gly, l-Ala, l-Leu, l-Phe) using the standard 1,3-dicyclohexylcarbodiimide (DCC), 1-hydroxybenzotriazole (HOBt) protocol. The compounds were fully characterized by a range of spectroscopic techniques including FAB-MS. The X-ray crystal structures of the parent para-(ferrocenyl)benzoyl methyl ester, Fc-C₆H₄CO₂Me, 1 and a chiral derivative N-{para-(ferrocenyl)benzoyl}-l-alanine methyl ester, Fc-C₆H₄CONHCH(CH₃)CO₂Me, 4 have been determined.     

A three-dimensional zincic molybdenum (V) phosphate with helical channel: Synthesis,structure, and electrochemical properties

A new reduced zincic molybdophosphate, (H₂bpp)₃[Zn₃Mo₁₂^VO₂₄(OH)₆(H₂O)₂(HPO₄)₆(PO₄)₂]·2H₂O 1 (bpp = 1,3-bis(4-pyridyl)propane) has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal space group I 41/a c d with a = 31.8033(4) Å, b = 31.8033(4) Å, c = 34.5593(8) Å, V = 34955.0(10) ų, and Z = 16 and exhibits a 4,6-connected 3-D framework with (3².8⁴)(3⁴.4².8³.9⁵.10) topology. The basic building blocks of [Zn(2)(Mo₆P₄)₂] are linked through [Zn(3)O₆] octahedra and [Zn(1)O₄] tetrahedra to construct 1-D chains along four different directions. Such 1-D chains are further connected by [Zn(1)O₄]²⁺ linkers to form a 3-D intricate framework with helical channels occupied by protonated bpp and water molecules. Additionally, the electrochemical property of the 1-CPE has been studied in detail.     

Binuclear rhodium(III) and iridium(III) monoselenocarboxylates: Synthesis,spectroscopy and structure of an ortho-metallated iridium complex featuring an IrCCC(μ-Se) chelate ring

Monoselenocarboxylate–bridged binuclear complexes of Rh^III and Ir^III, [(Cp1MCl)₂(μ-SeCOAr)₂] (1) (M = Rh or Ir; Cp1 = pentamethylcyclopentadienyl; Ar = Ph, C₆H₄Me–4), have been isolated either by the reaction between [Cp1₂M₂(μ-Cl)₂Cl₂] with KSeCOAr in acetonitrile or by treatment of [Cp1MCl(solvent)₂][PF₆] with KSeCOAr in acetone. The novel binuclear complexes, [Cp1IrCl(μ-SeCOAr)(κ²-SeCOC₆H₃R–)IrCp1] (2) (R = H or Me-4) with ortho-metallation at one of the iridium centres have been isolated following the use of excess AgPF₆. The single crystal structure of [Cp1IrCl(μ-SeCOC₆H₅)(κ²-SeCOC₆H₄–)IrCp1] (2a) exhibits two phenylcarboselenolate moieties situated in syn fashion with respect to the “Ir₂Se₂” plane, one of which leans towards the metal centre in order to undergo ortho-metallation after iridium–chlorine bond dissociation.     

Binuclear, 2D grid and 3D interlocking coordination polymers based on 1,2,4,5-benzenetetracarboxylic acid and 4,4′-azobispyridine

Three new nickel(II) complexes [Ni₂(btec)(azopy)₂(H₂O)₈]·2H₂O (1), {[Ni(H₂btec)(azopy)(H₂O)₂]·(azopy)}_n (2) and {[Ni₄(btec)₂(azopy)₃(H₂O)₁₀]·8H₂O}_n (3) (H₄btec = 1,2,4,5-benzenetetracarboxylic acid; azopy = 4,4′-azobispyridine) have been synthesized by tuning the reaction temperature and the metal–ligand ratio. They were characterized by single-crystal X-ray diffraction and elemental analysis. 1 shows a binuclear structure, 2 exhibits a 2D grid, and 3 features an interesting 3D framework with (6³)(4.6²)(4².6².8²) topology formed by two types of interlocked 2D layers.     

A novel three-dimensional 3d–4f heterometallic coordination polymer with unique (3,4)-connected topology and helical units: Synthesis,crystal structure and photoluminescence property

One new three-dimensional 3d–4f heterometallic coordination polymer, namely, {[EuZn₂(imdc)₂(C₂O₄)_0.5(H₂O)₄]·2H₂O}_n (1) (H₃imdc = imidazole-4,5-dicarboxylic acid), has been successfully synthesized by the hydrothermal reactions of Eu₂O₃, Zn(NO₃)₂·6H₂O, H₃imdc, H₂C₂O₄·2H₂O and H₂O. Single-crystal X-ray diffraction analysis reveals that complex 1 possesses 3D heterometallic framework containing 2D layer based on L–Zn2–L (L = imdc) helical chains and L–EuZn1–L chains. Complex 1 exhibits unprecedented (3,4)-connected four-nodal topology with Schläfli symbol (6·7·8) (6·7·9) (6·7²·8²·10) (7·8²). Moreover, the photoluminescence property of 1 was investigated in the solid-state at room temperature.     

One-dimensional nanoporous M2L2 rhombohedral molecular square with strong blue fluorescent emission

The hydrothermal reactions of Zn(ClO₄)₂ · 6H₂O and Cd(ClO₄)₂ · 6H₂O with the ligand N,N^′-bis(pyridylcarbonyl)-4,4^′-diaminodiphenyl ether (L) afford two one-dimensional (1D) coordination polymers, ([CdL(ClO₄)₂ · (H₂O)₂] · 2H₂O) (1) and [ZnL(ClO₄)₂ · (H₂O)₂] · 2H₂O, (2) having a nanoporous M₂L₂ rhombohedral molecular square with an approximately accessible cavity of 12.9 × 12.9 (1) and 12.7 × 12.7 (2) Å without any interpenetrations. Both 1 and 2 are isostructural and display very strong blue fluorescent emission in the solid state at room temperature.     

Two distinct ferroceneyl carboxylate Pb(II) complexes with the same composition prepared by two different synthetic methods: The substitution of precursor and one-pot reaction

Through substituation reaction, one lead ferroceneyl carboxylate polymer, namely [Pb(μ₂-OOCClH₃C₆Fc)₂(phen)]_n 1a [Fc = (η⁵-C₅H₅)Fe(η⁵-C₅H₄)] was synthesized from precursor [Pb(μ₂-η²-OOCClH₃C₆Fc)₂(CH₃OH)₂]_n 1. However, a mononuclear Pb(II) complex {[Pb(η²-OOCClH₃C₆Fc)₂(phen)]·(CH₃OH)·(H₂O)} 2 could be obtained from the traditional one-pot reaction of FcC₆H₃ClCOONa and Pb(OAc)₂ with 1,10-phenantholine (phen). The electrochemical studies of 1, 1a, 2 and FcC₆H₃ClCOOH indicate that the half-wave potentials of the ferrocenyl moieties in these complexes are all shifted to positive potential compared with that of FcC₆H₃ClCOOH.     

Reversible nitro–nitrito inter-conversion in a simple mono-nuclear nickel(II) complex [NiII{C6H4(NH2)2}2(NO2)2] in the solid state

A simple mono-nuclear nickel(II) complex [Ni^II{C₆H₄(NH₂)₂}₂(NO₂)₂] (1) has been synthesized from an aqueous solution containing nickel chloride, sodium nitrite and ortho-phenylenediamine (opda). When crystals of compound 1 are heated in the temperature range of 110–120 °C for 5 min, their brown color changes to blue, that is accompanied by the conversion of nitro group (N-coordinated) in compound 1 into nitrito group (O-coordinated) in compound [Ni^II{C₆H₄(NH₂)₂}₂(ONO)₂] (2). On cooling, the nitrito compound 2 goes back to parent nitro-compound 1.     

Tetra- and hexanuclear cage molecules based on diruthenium tetracarbonyl sawhorse units: Synthesis and molecular structure of [{Ru2(CO)4(PPh3)2}2(O2CCH2CO2)2] and [{Ru2(CO)4(PMe3)2}3(O2CC6H4CO2)3]

The thermal reaction of Ru₃(CO)₁₂ with malonic acid, followed by the addition of the corresponding ligand, yields the tetranuclear ruthenium complexes [{Ru₂(CO)₄L₂}₂(O₂CCH₂CO₂)₂] (L = PPh₃: 1, L = 3,5-Me₂NC₅H₃: 2), while the reaction of Ru₃(CO)₁₂ with terephthalic acid, followed by the addition of the corresponding ligand, gives rise to the formation of the hexanuclear ruthenium complexes [{Ru₂(CO)₄L₂}₃(O₂CC₆H₄CO₂)₃] (L = PMe₃: 3, L = 3,5-Me₂NC₅H₃: 4). The single-crystal X-ray structure analyses for 1 and 3, reveal both cages to consist of Ru₂(CO)₄ sawhorse units, 1 being a molecular loop, while 3 is a molecular triangle.     

X-ray single-crystal structure and magnetic properties of KMn(H2O)5Ru2(CO3)4·5H2O: A layered soft magnet

The temperature manipulation induces the aggregation of Ru₂(CO₃)₄^3 − paddle-wheel precursors and Mn^2 + ions in lower temperature ~ 10 °C forming layer structural complex, K[Mn(H₂O)₄Ru₂(CO₃)₄]·5H₂O (1). It composes of new negative layer {Mn(H₂O)₅Ru₂(CO₃)₄}_nⁿ⁻, and magnetic exchanges between spin centers result in ordering below 3.8 K. The observed critical temperature is like the previously reported 3D hetero-metallic carbonates H_0.3K_0.7Mn[Ru₂(CO₃)₄](H₂O)_5.5, which demonstrates that it is independent of the interlayer connecting in such heterometallic complexes based on square-grid layer {Ru₂(CO₃)₄}_n³ⁿ⁻.     

Catalytic hydroboration of vinylarenes using a zwitterionic arylspiroboronate ester iridium complex

Addition of B₂cat₃ (cat = 1,2-O₂C₆H₄) to Ir(acac)(dppb) (1; where dppb = 1,4-bis(diphenylphosphino)butane) gave the novel arylspiroboronate ester iridium complex Ir(η⁶-catBcat)(dppb) (2), the first example of an iridium compound containing a coordinating [Bcat₂]^? anion. Complex 2 is a remarkably selective catalyst precursor for the hydroboration of unhindered vinylarenes using pinacolborane.     

Thermal dehydration of Y(TFA)3(H2O)3: Synthesis and molecular structures of [Y(μ,η1:η1-TFA)3(THF)(H2O)]1∞ · THF and [Y4(μ3-OH)4(μ,η1:η1-TFA)6(η1-TFA)(η2-TFA)(THF)3(DMSO)(H2O)] · 6THF (TFA = trifluoroacetate)

In order to obtain a better anhydrous precursor for various applications in materials science and catalysis, thermal dehydration reactions of Y(TFA)₃(H₂O)₃ (TFA = trifluoroacetate) (A) were investigated. Thermal treatment of A at different temperatures under vacuum (5 × 10^?2 mm) for several hours failed to give totally anhydrous yttrium trifluoroacetate (as indicated by IR). Two different complexes, a partially dehydrated [Y(μ,η¹:η¹-TFA)₃(THF)(H₂O)]_1∞·THF (1) and a partially hydrolyzed [Y₄(μ₃-OH)₄(μ,η¹:η¹-TFA)₆(η¹-TFA)(η²-TFA)(THF)₃(DMSO)(H₂O)] · 6THF (2), were obtained with good and moderate yield, respectively, by crystallization of two different thermally treated batches of A from THF (or THF + DMSO) at room temperature. More efficient dehydration of A could be achieved at 200 °C in a furnace, the obtained anhydrous yttrium tris-trifluoroacetate giving Y(TFA)₃(THF)₂ (3) on crystallization from THF. All the products were characterized by elemental analyses, FT-IR and ¹H NMR spectroscopy as well as thermo-gravimetric analysis. In addition, single crystal X-ray structures are reported for 1 and 2, which show either a terminal (η¹ and η²) or bridging (μ,η¹:η¹) bonding behavior of the TFA ligand.     

A new organic-inorganic hybrid tetrameric polyoxometalate assembled by monovacant Dawson [α2-P2W17O61]10 − and trivalent cerium cations

A novel octa-nuclear cerium(III)-containing organic-inorganic hybrid polyoxometalate [N(CH₃)₄]₈H₁₆[{Ce(η¹-C₆H₅NO₂)₂(H₂O)₆[Ce(H₂O)₃(α₂-P₂W₁₇O₆₁)]}{Ce(η²-C₆H₅NO₂)₂(H₂O)₅[Ce(H₂O)(α₂-P₂W₁₇O₆₁)]}]₂·90H₂O (C₆H₅NO₂ = isonicotinic acid) (1) was obtained, which had been hydrothermally synthesized and characterized by IR spectrum, thermogravimetric analysis (TGA), and X-ray single-crystal diffraction. Structural analysis indicated at 1 is composed of four lacunary Dawson-type units [α₂-P₂W₁₇O₆₁]^10 − joined together by eight cerium cations forming an uncommon zigzag tetrameric structure with eight isonicotinic acids as the organic pendants coordinating to the cerium cations. Magnetic property studies indicate that obvious antiferromagnetic interactions exist in eight Ce^3 + cations.     

A MnII5 tetragonal pyramid stabilized by p-tert-butylcalix[8]arene: Synthesis,structure and magnetic property

A compound, [Mn₅(H₄C8A)(OH)₂(C₃H₆NO₂)(DMF)₅(CH₃O)_1.5(HCO₂) (C₂H₃O₂)_0.5]·2DMF·CH₃OH (1) (H₈C8A = p-tert-butylcalix[8]arene, DMF = N,N′-dimethylformamide), was synthesized by the solvothermal method in the mixed CH₃OH/DMF (1:1) solvent. Compound 1 is featured with a tetragonal pyramid-like Mn^II₅ cluster encircled within a calix[8]arene molecule with a ‘pleated loop’ conformation. Magnetic study indicates that the Mn^II centers exhibit antiferromagnetic interactions.     

1,1′-Ferrocene dicarboxylic acid pyridin-4-yl ester: A new bidentate ligand in arene ruthenium chemistry

1,1′-Ferrocene dicarboxylic acid pyridin-4-yl ester (1) is prepared from 1,1′-ferrocene dicarbonyl chloride and 4-hydroxypyridine. This new bidentate ferrocenoyl ligand reacts with the monocationic complex [(η⁶-p-cymene)₂Ru₂(μ-OH)₃]⁺ to give the dicationic complex [(η⁶-p-cymene)₂Ru₂(μ-OH)₂(1,1′- (NC₅H₄–OOC)₂–Fc)]²⁺ (2) (Fc: C₅H₄–Fe–C₅H₄), isolated as a tetrafluoroborate salt. The single-crystal X-ray structure analysis of [2][BF₄]₂ reveals the ferrocenoyl pyridine ligand 1 to act as μ₂-η² chelating ligand in the dinuclear complex, having replaced a μ₂-η¹-hydroxo ligand.     

Ligand concentration and reaction time controlled successive substitution of chloro and η6-benzene of di-μ-chlorobis{η6-benzene)dichlororuthenium(II)} with selenated Schiff base: Formation of half sandwich Ru(II) complex highly active catalyst for oxidation of alcohols

Schiff base (L) synthesized by reacting 2-methylthiobenzeldehyde with 2-(phenylseleno)ethylamine on reaction with di-μ-chlorobis{η⁶-benzene)dichloro-ruthenium(II)}(a) forms two type of species: (i) [Ru(L)₂][PF₆]₂ (1) [L:a = 4:1 and reaction time ～8 h] and (ii) [Ru(η⁶-C₆H₆)(L)][PF₆]₂ (2) [L:a = 2:1 and reaction time ～1 h]. This is first example in which chloro as well benzene ring both are successively substituted by controlling metal:ligand ratio and duration of reaction. The geometry around Ru in complex 1 is distorted octahedral. The 2 has a pseudo-octahedral half sandwich “piano-stool” disposition of ligands around Ru. The Ru–Se distances are 2.4683(10)–2.5082(7) ?. The proton and carbon-13 NMR spectra of L and its both complexes 1 and 2 authenticate them. The 2 shows high catalytic activity for oxidation of primary and secondary alcohols both (TON upto 9.6 × 10⁴; TOF upto 4.80 × 10⁴ h^?1).     

Two phenoxo-O bridged Dy2 complexes based on 8-hydroxyquinolin derivatives with different magnetic relaxation features

Two new dinuclear dysprosium compounds, namely, [Dy₂(L1)₂(hfac)₆]·C₇H₁₆ (1) and [Dy₂(L2)₂(hfac)₆]·C₇H₁₆ (2) (HL1 = 5-(2-thenylidene)-8-hydroxylquinoline; HL2 = 5-(4-methoxylbenzylidene)-8-hydroxylquinoline; hfac = hexafluoroacetylacetonate) have been successfully obtained via applying two different ligands, and further characterized by crystallography. Structural analysis shows that both of 1 and 2 possess a four-membered [Dy₂O₂] core with similar coordination pockets. The center Dy(III) ions in 1 and 2 are all completed by eight coordination environments with O₈ set. Interestingly, the different features of ligand HL1 and HL2 result in their different magnetic relaxation behaviors with the energy barrier of 6.81 K for 1 and 0.72 K for 2.