The Effect of SiMe3 and SiEt3 Para Substituents for High Activity and Introduction of a Hydroxy Group in Ethylene Copolymerization Catalyzed by Phenoxide-Modified Half-Titanocenes

Remarkable effects of SiMe₃ and SiEt₃ para-substituents in the phenoxide-modified half-titanocenes, Cp*TiCl₂(O-2,6-ⁱPr₂-4-R-C₆H₂) [R=SiMe₃ ( 6 ), SiEt₃ ( 7 )], toward the catalytic activities in ethylene copolymerizations with 2-methyl-1-pentene, 1-decene, 1-dodecene and with 9-decen-1-ol (DC-OH) have been demonstrated. The activities by 6 , 7 at 50 °C showed higher than those conducted at 25 °C in all cases in the presence of MAO cocatalyst. Efficient synthesis of high-molecular-weight (HMW) ethylene copolymers incorporating DC-OH (or 5-hexen-1-ol, HX-OH) has been attained in the copolymerization by 7 , which showed better DC-OH (HX-OH) incorporation at 50 °C to afford the HMW copolymers, poly(ethylene-co-DC-OH)s, with high activities (activity 1.21–3.81×10⁵ kg-polymer mol⁻¹-Ti h, M_n=6.55–10.0×10⁴, DC-OH 2.3–3.6 mol %).     

Bonding in Barium Boryloxides,Siloxides, Phenoxides and Silazides: A Comparison with the Lighter Alkaline Earths

Barium complexes ligated by bulky boryloxides [OBR₂]⁻ (where R=CH(SiMe₃)₂, 2,4,6-ⁱPr₃-C₆H₂ or 2,4,6-(CF₃)₃-C₆H₂), siloxide [OSi(SiMe₃)₃]⁻, and/or phenoxide [O-2,6-Ph₂-C₆H₃]⁻, have been prepared. A diversity of coordination patterns is observed in the solid state for both homoleptic and heteroleptic complexes, with coordination numbers ranging between 2 and 4. The identity of the bridging ligand in heteroleptic dimers [Ba(μ₂-X₁)(X₂)]₂ depends largely on the given pair of ligands X₁ and X₂. Experimentally, the propensity to fill the bridging position increases according to [OB{CH(SiMe₃)₂}₂)]⁻<[N(SiMe₃)₂]⁻<[OSi(SiMe₃)₃]⁻<[O(2,6-Ph₂-C₆H₃)]⁻<[OB(2,4,6-ⁱPr₃-C₆H₂)₂]⁻. This trend is the overall expression of 3 properties: steric constraints, electronic density and σ- and π-donating capability of the negatively charged atom, and ability to generate Ba ⋅ ⋅ ⋅ F, Ba ⋅ ⋅ ⋅ C(π) or Ba ⋅ ⋅ ⋅ H−C secondary interactions. The comparison of the structural motifs in the complexes [Ae{μ₂-N(SiMe₃)₂}(OB{CH(SiMe₃)₂}₂)]₂ (Ae = Mg, Ca, Sr and Ba) suggest that these observations may be extended to all alkaline earths. DFT calculations highlight the largely prevailing ionic character of ligand-Ae bonding in all compounds. The ionic character of the Ae-ligand bond encourages bridging coordination, whereas the number of bridging ligands is controlled by steric factors. DFT computations also indicate that in [Ba(μ₂-X₁)(X₂)]₂ heteroleptic dimers, ligand predilection for bridging vs. terminal positions is dictated by the ability to establish secondary interactions between the metals and the ligands.     

Tetraazadibora[3, 3]paracyclophane

Starting from the para‐phenylenediamine derivative HN(SiMe₃)‐C₆H₄‐NH(SiMe₃), a lithiation and subsequent borylation give [(MeO)₂B]N(SiMe₃)‐C₆H₄‐N(SiMe₃)[B(OMe)₂] ( 1 ), the hydridation of which yields Li₂[(H₃B)N(SiMe₃)‐C₆H₄‐N(SiMe₃)(BH₃)] ( 2 ). Applying ZrCl₄ upon 2 initiates a condensation to give the title compound [‐N(SiMe₃)‐p‐C₆H₄‐N(SiMe₃)‐BH‐]₂, a hetero[3, 3]paracyclophane with two N‐B‐N chains that connect the para‐phenylene units. The product 3 crystallizes in the orthorhombic space group P2₁2₁2₁.     

Metallorganische Verbindungen der Lanthanoide. 155 [1] Synthese und Charakterisierung neuer Lanthanoidocen‐Komplexe mit silylierten Cyclopentadienylliganden

Organometallic Compounds of the Lanthanides. 155 [1] Synthesis and Characterization of New Lanthanocene Complexes containing Silylated Cyclopentadienyl Ligands The trichlorides of yttrium, samarium, and lutetium react with two equiv. of K[C₅H₄SiEt₃] ( 1 ) to form the dimeric compounds [(η⁵‐C₅H₄SiEt₃)₂LnCl]₂ (Ln = Y ( 2 ), Sm ( 3 ), Lu ( 4 )). These react with one equiv. of methyllithium to give the corresponding dimeric lanthanocenemethyl complexes [(η⁵‐C₅H₄SiEt₃)₂LnMe]₂ (Ln = Y ( 5 ), Sm ( 6 ), Lu ( 7 )). The reaction between samarium trichloride and lutetium trichloride, respectively with two equiv. of K[1, 3‐C₅H₃(SiMe₃)₂] followed by one equiv. of methyllithium results in the formation of the monomeric methyl complexes [η⁵‐1, 3‐C₅H₃(SiMe₃)₂]₂LnMe(THF) (Ln = Sm ( 8 ), Lu ( 9 )). The new compounds have been characterized by elemental analysis, mass spectrometry, ¹H‐ and ¹³C{¹H} NMR spectroscopy, as well as 1 — 7 by single crystal X‐ray structure analysis.     

Katalysatordesaktivierungen bei der Acetylen-Polymerisation mit Titanocen- bzw. Zirconocen-Komplexen des Bis(trimethylsilyl)acetylens

Desactivation of Catalysts in the Polymerization of Acetylene by Bis(trimethylsilyl)acetylene Complexes of Titanocene or Zirconocene Unexpected inactive byproducts were observed in the catalytic polymerization of acetylene using metallocene alkyne complexes Cp₂M(L)(η²-Me₃SiC₂SiMe₃), 1 : M = Ti, without L; 2 : M = Zr, L = thf. The reaction of 1 was investigated in detail by NMR to give quantitatively at –20 °C the titanacyclopentadiene Cp₂Ti–CH=CH–C(SiMe₃)=C(SiMe₃) ( 3 ). Around 0 °C 3 starts to rearrange to yield the dihydroindenyl complex 4 via coupling of one Cp-ligand with the titanacyclopentadiene. In the reaction of 2 under analogous conditions a zirconacyclopentadiene Cp₂Zr–CH=CH–C(SiMe₃)=C(SiMe₃) ( 5 ) and the dimeric complex [Cp₂Zr(C(SiMe₃)=CH(SiMe₃)]₂[μ-σ(1,2)-C≡C] ( 6 ) were observed. Whereas 5 decomposes to a mixture of unidentified paramagnetic species, 6 was isolated and investigated by NMR spectroscopy and X-ray analysis. In the reaction of rac-(ebthi)Zr(η²-Me₃SiC₂SiMe₃) (ebthi = ethylenbistetrahydroindenyl) with 2-ethynyl-pyridine the complex rac-(ebthi)ZrC(SiMe₃)=CH(SiMe₃)](σ-C≡CPy) 7 was obtained, which was investigated by an X-ray analysis.     

Reactivity of the Bicyclic Amido-Substituted Silicon(I) Ring Compound Si4{N(SiMe3)Mes}4 with FLP-Type Character

The bicyclic amido-substituted silicon(I) ring compound Si₄{N(SiMe₃)Mes}₄ 2 (Mes=Mesityl=2,4,6-Me₃C₆H₂) features enhanced zwitterionic character and different reactivity from the analogous compound Si₄{N(SiMe₃)Dipp}₄ 1 (Dipp=2,6-ⁱPr₂C₆H₃) due to the smaller mesityl substituents. In a reaction with the N-heterocyclic carbene NHC (1,3,4,5-tetramethyl-imidazol-2-ylidene), we observe adduct formation to give Si₄{N(SiMe₃)Mes}₄ ⋅ NHC ( 3 ). This adduct reacts further with the Lewis acid BH₃ to yield the Lewis acid–base complex Si₄{N(SiMe₃)Mes}₄ ⋅ NHC ⋅ BH₃ ( 4 ). Coordination of AlBr₃ to 2 leads to the adduct 5 . Calculated proton affinities and fluoride ion affinities reveal highly Lewis basic and very weak Lewis acidic character of the low-valent silicon atoms in 1 and 2 . This is confirmed by protonation of 1 and 2 with Brookharts acid yielding 6 and 7 . Reaction with diphenylacetylene only occurs at 111 °C with 2 in toluene and is accompanied by fragmentation of 2 to afford the silacyclopropene 8 and the trisilanorbornadiene species 9 .     

Substituent Effect on the Electronic Properties and Nature of the W≡C Bond in trans‐Cl(OC)(H3P)3W(≡C‐para‐C6H4X) (X = H,F, SiH3, CN,NO2, SiMe3, CMe3, NH2, NMe2) Complexes: A Computational Quantum Chemistry Study

In this investigation, we describe substituent effect on the dipole moment, ionization potential, electron affinity, structure, frontier orbitals energy, in the trans‐Cl(OC)(H₃P)₃W(≡C‐para‐C₆H₄X) (X = H, F, SiH₃, CN, NO₂, SiMe₃, CMe₃, NH₂, NMe₂) complexes using MPW1PW91 quantum chemical calculations. The nature of chemical bond between the [Cl(OC)(H₃P)₃W]⁻ and [C‐para‐C₆H₄X]⁺ fragments was illustrated with energy decomposition analysis (EDA). Percentage composition in terms of the defined groups of frontier orbitals for these complexes was inspected to investigate the character in metal–ligand bonds. Quantum theory of atoms in molecules (QTAIM) was used for illustration of metal–ligand bonds in these complexes.     

Highly Active,Low‐Valence Molybdenum‐ and Tungsten‐Amide Catalysts for Bifunctional Imine‐Hydrogenation Reactions

The reactions of [M(NO)(CO)₄(ClAlCl₃)] (M=Mo, W) with (iPr₂PCH₂CH₂)₂NH, (PN^HP) at 90 °C afforded [M(NO)(CO)(PN^HP)Cl] complexes (M=Mo, 1a ; W, 1b ). The treatment of compound 1a with KOtBu as a base at room temperature yielded the alkoxide complex [Mo(NO)(CO)(PN^HP)(OtBu)] ( 2a ). In contrast, with the amide base Na[N(SiMe₃)₂], the PN^HP ligand moieties in compounds 1a and 1b could be deprotonated at room temperature, thereby inducing dehydrochlorination into amido complexes [M(NO)(CO)(PNP)] (M=Mo, 3a ; W, 3b ; PNP=(iPr₂PCH₂CH₂)₂N)). Compounds 3a and 3b have pseudo‐trigonal‐bipyramidal geometries, in which the amido nitrogen atom is in the equatorial plane. At room temperature, compounds 3a and 3b were capable of adding dihydrogen, with heterolytic splitting, thereby forming pairs of isomeric amine‐hydride complexes [Mo(NO)(CO)H(PN^HP)] ( 4a(cis) and 4a(trans) ) and [W(NO)(CO)H(PN^HP)] ( 4b(cis) and 4b(trans) ; cis and trans correspond to the position of the H and NO groups). H₂ approaches the Mo/W?N bond in compounds 3a , 3b from either the CO‐ligand side or from the NO‐ligand side. Compounds 4a(cis) and 4a(trans) were only found to be stable under a H₂ atmosphere and could not be isolated. At 140 °C and 60 bar H₂, compounds 3a and 3b catalyzed the hydrogenation of imines, thereby showing maximum turnover frequencies (TOFs) of 2912 and 1120 h^?1, respectively, for the hydrogenation of N‐(4 ‐ methoxybenzylidene)aniline. A Hammett plot for various para‐substituted imines revealed linear correlations with a negative slope of ?3.69 for para substitution on the benzylidene side and a positive slope of 0.68 for para substitution on the aniline side. Kinetics analysis revealed the initial rate of the hydrogenation reactions to be first order in c(cat.) and zeroth order in c(imine). Deuterium kinetic isotope effect (DKIE) experiments furnished a low k_H/k_D value (1.28), which supported a Noyori‐type metal–ligand bifunctional mechanism with H₂ addition as the rate‐limiting step.     

Zur Bildung cyclischer Silylphosphane Umsetzung von Li-Phosphiden mit R2SiCl2 (R = Me,Et, t-Bu)

Formation of Cyclic Silylphosphanes. Reaction of Li-Phosphides with R₂SiCl₂ (R? Me, Et, t-Bu) The reaction of Me₂SiCl₂ with Li-phosphides (mixture of LiPH₂, Li₂PH) leads to the formation of Me₂Si(PH₂)Cl 1 , Me₂Si(PH₂)₂ 2 , H₂P? SiMe₂? PH? SiMe₂Cl 3 , (H₂P? SiMe₂)₂PH 4 , (HP? SiMe₂)₃ 6 , 5 , 7 , 8 , 9 , 10 , 40 . Excess of phosphides in Et₂O – as well as excess of LiPH₂ – favourably forms 10 . Li₂PH (virtually free of Li₃P and LiPH₂) is obtained by reaction of LiPH₂ · DME with LiBu; Li₃P by reaction of PH₃ with LiBu in toluene. Isomerization by Li/H migration determines the course of reaction of the PH-bearing compounds with Li-phosphides. With Me₂SiCl₂ Li₃P mainly generates compound 10 . The reaction of the Li-phosphides with Et₂SiCl₂ mainly leads to (HP? SiEt₂)₃ 18 and (HP? SiEt₂)₂ 17 as well as to Et₂Si(PH₂)Cl 11 , Et₂Si(PH₂)₂ 12 , (ClEt₂Si)₂PH 13 , H₂P? SiEt₂? PH? SiEt₂Cl 14 , (H₂P? SiEt₂)₂PH 15 and 16 . In the reaction with LiPH₂ · DME the same compounds are obtained and isomerization by Li/H migration (formation of PH₃) already begins at ?70°C. In toluene ClEt₂Si? P(SiEt₂)₂P? SiEt₂Cl is additionally formed. Derivatives of 9, 10, 40 are not observed. The reaction of (t-Bu)₂SiCl₂ with LiPH₂ leads to HP[Si(t-Bu)₂]₂PH 20 (yield 76%) and formation of PH₃, the reaction with Li₂PH to 20 (54%) besides HP[Si(t-Bu)₂]₂PLi 21 .     

Polymerization of Si-containing acetylenes. XIV. Polymerization of diphenylacetylenes with bulky silyl groups and polymer properties

Polymerization and polymer properties of diphenylacetylenes with bulky silyl groups (SiMe₂–i-Pr, SiMe₂–t-Bu, SiMe₂Ph, SiEt₃) at para or meta position were studied under comparison with those of the SiMe₃ derivatives. The present monomers polymerized in good yields with TaCl₅-cocatalysts to form high molecular-weight polymers (M _w > 4 × 10⁵). The polymer yields of para-substituted monomers were similar to that of the SiMe₃ derivative, while those of meta substituted monomers were lower than that of m-SiMe₃ derivative. Most of the polymers were totally soluble in common solvents such as toluene and CHCl₃, although the polymers with p-SiMe₂–t-Bu and p-SiMe₂Ph groups were partly insoluble in all solvents. These polymers resembled SiMe₃-containing homologues in the UV-visible absorption and thermal stability. The oxygen permeability coefficients of these polymers were in the range of 10^?9?10^?8 cm³ (STP) cm/(cm²·s cm Hg)—lower than those of the corresponding SiMe₃-containing polymers. © 1993 John Wiley & Sons, Inc.     

Determination of gas-phase acidities of dimethylphenols: Combined experimental and theoretical study

The gas-phase acidities of the six dimethylphenol isomers were determined experimentally, by using the kinetic method, and theoretically, through quantum chemistry calculations. The experimental values, relative to the gas-phase acidity of phenol, are (in kJ mol⁻¹): −1.76 ± 0.76 (2,3-Me₂C₆H₃OH), 1.78 ± 0.29 (2,4-Me₂C₆H₃OH), 0.83 ± 0.58 (2,5-Me₂C₆H₃OH), −4.39 ± 0.89 (2,6-Me₂C₆H₃OH), 5.38 ± 1.08 (3,4-Me₂C₆H₃OH), and 1.88 ± 0.08 (3,5-Me₂C₆H₃OH). This trend was discussed by considering the substituent effects on the thermodynamic stabilities both of the parent phenols and the corresponding phenoxide ions. The above acidity data, the literature values for 2-, 3-, and 4-methylphenol, and the substituent effects analysis allowed to develop a simple empirical method to estimate the acidity of any methyl-substituted phenol.     

Synthesis of Diaminophosphonium Salts [Ph2(ArNH)2P]+Br− (Ar = o-MeC6H4, p-MeC6H4, p-Pr i C6H4, p-EtO2CC6H4, p-MeOC6H4)

The behavior of different anilines H₂NC₆H₄R (R = o-Me, p-Me, o-, m- and p? ⁱ Pr, p-OMe, p-CO₂Et) and 2,6-Me₂C₆H₃NH₂ towards trihalophosphoranes was studied. 2,6-Me₂C₆H₃NH₂ failed to form the diaminophosphonium salt [Ph₂PNH(2,6-Me₂C₆H₃)₂]Br, and the aminophosphine oxide Ph₂(2,6-Me₂C₆H₃NH)PO was the only isolated product. Both o- and p-toluidine gave the corresponding diaminophosphonium salts; however in the case of o-toluidine, the yield was low and a mixture with the respective aminophosphine oxide was observed. Anilines containing methoxy and ethoxycarbonyl groups in para-position form the diaminophosphonium salts in reasonable yields.     

Elementorganische Amin/Imin-Verbindungen,XXXI. Cyclometallierung bei N-tert-Butyl-Phosphor-Stickstoff-Iridiumkomplexen

Element-Organic Amine/Imine Compounds, XXXI. - Cyclometallation with N-tert-Butyl-Phosphorus-Nitrogen Iridium Complexes The interaction of R¹R²N–PNR³ ( 1 ) (R¹  SiMe₃, tBu, iC₃H₇; R²  R³  SiMe₃, tBu) with [M(COD)(μ-Cl)]₂ ( 2 ), M  Rh, Ir, affords the amino(imino)phosphane complexes 3 , whose PN bond adds methanol with formation of the diamidophosphite complexes 4 . Already below 0°C the iridium compounds of 4 undergo cyclometallation of a tBu methyl group (R²) with formation of the hydrido-iridium metallaheterocycles 5 . The structures of 4b and 5a are elucidated by X-ray analyses.     

Alternating copolymerization of cyclohexene oxide and carbon dioxide catalyzed by noncyclopentadienyl rare‐earth metal bis(alkyl) complexes

The syntheses of several dialkyl complexes based on rare‐earth metal were described. Three β‐diimine compounds with varying N‐aryl substituents (HL¹=(2‐CH₃O(C₆H₄))N?C(CH₃)CH?C(CH₃)NH(2‐CH₃O(C₆H₄)), HL² = (2,4,6‐(CH₃)₃ (C₆H₂))N?C(CH₃)CH?C(CH₃)NH(2,4,6‐(CH₃)₃(C₆H₂)), HL³ = PhN?C(CH₃)CH(CH₃) NHPh) were treated with Ln(CH₂SiMe₃)₃(THF)₂ to give dialkyl complexes L¹Ln (CH₂SiMe₃)₂ (Ln = Y ( 1a ), Lu ( 1b ), Sc ( 1c )), L²Ln(CH₂SiMe₃)₂(THF) (Ln = Y ( 2a ), Lu ( 2b )), and L³Lu(CH₂SiMe₃)₂(THF) (3). All these complexes were applied to the copolymerization of cyclohexene oxide (CHO) and carbon dioxide as single‐component catalysts. Systematic investigation revealed that the central metal with larger radii and less steric bulkiness were beneficial for the copolymerization of CHO and CO₂. Thus, methoxy‐modified β‐diiminato yttrium bis(alkyl) complex 1a , L¹Y(CH₂SiMe₃)₂, was identified as the optimal catalyst, which converted CHO and CO₂ to polycarbonate with a TOF of 47.4 h^?1 in 1,4‐dioxane under a 15 bar of CO₂ atmosphere (T_p=130 °C), representing the highest catalytic activity achieved by rare‐earth metal catalyst. The resultant copolymer contained high carbonate linkages (>99%) with molar mass up to 1.9 × 10⁴ as well as narrow molar mass distribution (M_w/M_n = 1.7). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6810–6818, 2008     

Synthesis of bromine-functionalized polyolefins by scandium-catalyzed copolymerization of 10-bromo-1-decene with ethylene,propylene, and dienes

By use of a THF-containing trimethylsilylmethyl scandium catalyst system (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF)/[Ph₃C][B(C₆F₅)₄], the multi-component copolymerization of 10-bromo-1-decene (BrDC) with ethylene, propylene, and dienes has been achieved to afford a new family of bromine-functionalized polyolefins with controllable composition and high molecular weight. The copolymerization of BrDC with ethylene afforded the well-defined BrDC–ethylene copolymers with high BrDC incorporation (up to 12 mol%) and high molecular weight (M_w > 100 kg mol⁻¹). The terpolymerization of propylene, ethylene with BrDC afforded random ethylene–propylene–BrDC terpolymers with controllable bromine content (2 ~ 11 mol%), high molecular weight (M_w > 100 kg mol⁻¹) and low glass transition temperature (T_g = −51 °C ~ −67 °C). Moreover, the tetrapolymerization of ethylene, propylene, BrDC, and ethylidene norbornene or conjugated dienes such as isoprene and myrcene has been achieved for the first time to afford selectively the bromine-functionalized ethylene–propylene–diene rubbers containing various types of double bonds.     

Neue Aminometallane des Aluminiums und Galliums

New Aminometalanes of Aluminum and Gallium The reaction of secondary amines R′RNH with trimethyaluminum leads to the formation of dimeric aminoalanes [RR′NAlMe₂]₂ ( 1 ) (R = 2,6-Me₂C₆H₃, R′ = SiMe₂(2,4,6-Me₃C₆H₂)) and 2 (R = Ph, R′ = SiMe₃). Using a different stoichiometric ratio, a monomeric aminoalane [RR′N]₂AlMe ( 3 ) (R = Ph, R′ = SiPh₂Me) is obtained, having an aluminum atom of coordination number three due to the steric demand of the substituents. The synthesis of the corresponding aminogallanes 4 , 5 and 6 is achieved by reaction of lithium amides LiNRR′ (R = Ph, 2,6-iPr₂C₆H₃; R′ = SiMe₃, SiMe₂iPr) with dimethylgalliumchloride, Me₂GaCl, in n-hexane. The formation of the dimeric species is in 1 through carbon while that in 2 and 3 is formed through nitrogen. The X-ray single crystal structure analysis of 1 , 2 , 3 and 4 are reported.     

Synthesis and Structural Characterization of Some Novel Trialkylsilyl‐substituted Lithium Benzyl Complexes [Li(tmeda)][CHRSiMe2R′] (R = Ph, 3,5‐Me2C6H3; R′ = Me,tBu, Ph)

The reactions of PhCH₂SiMe₃ ( 1 ), PhCH₂SiMe₂^tBu ( 2 ), PhCH₂SiMe₂Ph ( 3 ), 3,5‐Me₂C₆H₃CH₂SiMe₃ ( 4 ), and 3,5‐Me₂C₆H₃CH₂SiMe₂^tBu ( 5 ) with ⁿBuLi in tetramethylethylenediamine (tmeda) afford the corresponding lithium complexes [Li(tmeda)][CHRSiMe₂R′] (R, R′ = Ph, Me ( 6 ), Ph, ^tBu ( 7 ), Ph, Ph ( 8 ), 3,5‐Me₂C₆H₃, Me ( 9 ), and 3,5‐Me₂C₆H₃, ^tBu ( 10 )), respectively. The new compounds 5 , 7 , 8 , 9 and 10 have been characterized by ¹H and ¹³C NMR spectroscopy, compounds 7 , 8 and 9 also by X‐ray structure analysis.     

Effect of Axial Ligands on Easy-Axis Anisotropy and Field-Induced Slow Magnetic Relaxation in Heptacoordinated FeII Complexes

A rational approach to modulating easy-axis magnetic anisotropy by varying the axial donor ligand in heptacoordinated Fe^II complexes has been explored. In this series of complexes with formulae of [Fe(H₄L)(NCS)₂] ⋅ 3 DMF ⋅ 0.5 H₂O ( 1 ), [Fe(H₄L)(NCSe)₂] ⋅ 3 DMF ⋅ 0.5 H₂O ( 2 ), and [Fe(H₄L)(NCNCN)₂] ⋅ DMF ⋅ H₂O ( 3 ) [H₄L=2,2′-{pyridine-2,6-diylbis(ethan-1-yl-1-ylidene)}bis(N-phenylhydrazinecarboxamide)], the axial positions are successively occupied by different nitrogen-based π-donor ligands. Detailed dc and ac magnetic susceptibility measurements reveal the existence of easy-axis magnetic anisotropy for all of the complexes, with 1 [U_eff=21 K, τ₀=1.72×10⁻⁶ s] and 2 [U_eff=25 K, τ₀=2.25×10⁻⁶ s] showing field-induced slow magnetic relaxation behavior. However, both experimental studies and theoretical calculations indicate the magnitude of the D value of complex 3 to be larger than those of complexes 1 and 2 due to the axial bond angle being smaller than that for an ideal geometry. Detailed analysis of the field and temperature dependences of relaxation time for 1 and 2 has revealed that multiple relaxation processes (quantum tunneling of magnetization, direct, and Raman) are involved in slow magnetic relaxation for both of these complexes. Magnetic dilution experiments support the role of intermolecular short contacts.     

Intrinsic Molybdenum-Based POMOFs with Impressive Gas Adsorptions and Photochromism

Novel molybdenum(VI/V) POM-based self-constructed frameworks [Mo^VI₁₂O₂₄(μ₂-O)₁₂(trz)₆(H₂O)₆] ⋅ 6Hma ⋅ 18H₂O ( 1 , Htrz=1H-1,2,3-triazole, ma=methylamine), [Mo^VI₇O₁₄(μ₂-O)₈(trz)₅(H₂O)] ⋅ 7Hma ⋅ 5H₂O ( 2 ), Na₃[Mo^V₆O₆(μ₂-O)₉(Htrz)₃(trz)₃] ⋅ 7.5H₂O ( 3 ) and [Mo^V₈O₈(μ₂-O)₁₂(Htrz)₈] ⋅ 30H₂O ( 4 ) have been covalently decorated with tri-coordinated deprotonated/protonated 1,2,3-triazoles. Channels with an inner diameter of 7.5 Å were found in 1 , whereas a tunnel composed of stacking molecules with an inner diameter of 4.1 Å along the b-axis exists in 2 ; it is occupied by free disordered methylamines, showing selective adsorption of O₂ and CO₂ at 25 °C. Obvious downfield shifts were observed by ¹³C NMR spectroscopies for methylamines inside the confined channels in 1 and 2 . There are diversified pores in 3 and 4 , which are formed by the molecules themselves and intermolecular accumulations. Adsorption tests indicate that 3 and 4 are fine adsorption materials for CH₄ and CO₂ under low pressure that rely on the environments built by the POMs. Correspondingly, 1 and 2 display reversible photoresponsive thermochromism that is subtlety influenced by the channels. The polyoxometalate organic frameworks (POMOFs) with multiple functional adsorptions are easy to assemble. Their photo-/thermoresponse properties offer a new pathway for the self-constructions of one-off hybrid materials that possess the good properties of both POMs and MOFs.     

Efficient and Recyclable RuCl3 ⋅ 3H2O Catalyst Modified with Ionic Diphosphine for the Alkoxycarbonylation of Aryl Halides

A series of ionic (mono-/di-)phosphines ( L2 , L4 , and L6 ) with structural similarity and their corresponding neutral counterparts ( L1 , L3 , and L5 ) were applied to modulate the catalytic performance of RuCl₃ ⋅ 3H₂O. With the involvement of the ionic diphosphine ( L4 ), in which the two phosphino-fragments were linked by butylene group, RuCl₃ ⋅ 3H₂O with advantages of low cost, robustness, and good availability was found to be an efficient and recyclable catalyst for the alkoxycarbonylation of aryl halides. The L4 -based RuCl₃ ⋅ 3H₂O system corresponded to the best conversion of PhI (96 %) along with 99 % selectivity to the target product of methyl benzoate as well as the good generality to alkoxycarbonylation of different aryl halides (ArX, X=I and Br) with alcohols MeOH, EtOH, i-PrOH and n-BuOH. The electronic and steric effects of the applied phosphines, which were analyzed by the ³¹P NMR for ¹J³¹_P-⁷⁷_Se¹J measurement and single-crystal X-ray diffraction, were carefully co-related to the performance RuCl₃ ⋅ 3H₂O catalyst. In addition, the L4 -based RuCl₃ ⋅ 3H₂O system could be recycled successfully for at least eight runs in the ionic liquid [Bmim]PF₆.