Synthesis and Crystal Structure of Borate Oxide Co_3BO_5

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Mo2B4O9—Connecting Borate and Metal-Cluster Chemistry

We report on the first thoroughly characterized molybdenum borate, which was synthesized in a high-pressure/high-temperature experiment at 12.3 GPa/1300 °C using a Walker-type multianvil apparatus. Mo₂B₄O₉ incorporates tetrahedral molybdenum clusters into an anionic borate crystal structure—a structural motif that has never been observed before in the wide field of borate crystal chemistry. The six bonding molecular orbitals of the [Mo₄] tetrahedron are completely filled with 12 electrons, which are fully delocalized over the four molybdenum atoms. This finding is in agreement with the results of the magnetic measurements, which confirmed the diamagnetic character of Mo₂B₄O₉. The two four-coordinated boron sites can be differentiated in the ¹¹B MAS-NMR spectrum because of the strongly different degrees of local distortions. Experimentally obtained IR and Raman bands were assigned to vibrational modes based on DFT calculations.     

Borate,lithium borate,and borophosphate powders by sol–gel precipitation

Borate, lithium borate and borophosphate powders were synthesized by the sol–gel method. Triethyl borate, lithium methoxide, and orthophosphoric acid were used as precursors for B₂O_3, Li₂O, and P₂O₅, respectively. Powders were characterized by FTIR, DTA, XRD and SEM techniques. Powders from the Li₂O–B₂O₃ system exhibited glassy features while borate and borophosphate powders contained mainly crystalline B₂O₃ according to XRD analysis. However, a 500 °C heat treatment transformed these crystalline powders into glass powders. Conversely, heat treatment of Li₂O–B₂O₃ powders transformed their structure from glassy to crystalline (Li₂B₄O₇). Chemical durability studies conducted in water at 60 °C showed that minor additions of P₂O₅ into borate and lithium borate powders improved their chemical durability significantly. Furthermore, Li₂O and P₂O₅ acted synergistically on the chemical durability when added simultaneously to borate compositions.     

Esterification of Carboxylic Acids and Diacids by Trialkyl Borate under Solvent- and Catalyst-Free Conditions

Esterification or transesterification reactions are usually carried out in the presence of homogeneous or heterogeneous catalysts. However, recently a new method was reported for the esterification of carboxylic acids by tributyl borate under solvent- and catalyst-free conditions. In order to show the synthetic ability of trialkyl borate esters in the esterification reactions, here, the esterification of other carboxylic acids and diacids by tributyl-, triisoamyl-, and tribenzyl borate under the same conditions were reported. Some of the prepared ester and diester products have found wide applications as plasticizers and synthetic ester base lubricants. The esterification reactions have been cleanly carried out in the absence of any solvent under catalyst-free conditions. The maximum rate belongs to isoamyl trichloroacetate （VIb） which reached about 76% within about 6.5 h. On the basis of obtained findings, it seems that electron withdrawing groups on carboxylic acid facilitate the esterification reaction.     

Crystal Structure of Lithium Yttrium Borate LiY6O5（BO3）3

1 INTRODUCTION In recent years, more and more attention has been paid to rare-earth borates due to their excellent pro- perties, such as YCa4O(BO3)3(YCOB)[1], YAl3(BO3)4 (YAB)[2] and La2CaB10O19[3] for nonlinear optical materials and self-frequency doubling materials as well as YBO3:Eu for red phosphor materials[4] and Li6M1-xCex(BO3)3 (M = Y, Gd) for neutron detec- tors[5]. In this work, we focus our research interest on LiY6O5(BO3)3 as hosts for VUV (vacuum ultraviolet) l…     

Syntheses and Structures of Facial and Meridional Stereoisomers of κ2-N,S-Chelated Ruthenium Borate Complexes

The trans-mer-[(κ²-N,S-NS₂C₇H₄)PR₃Ru{κ³-H,S,S′-H₂B (NS₂C₇H₄)₂}], (trans-mer -1 a : R=Cy; trans-mer -1 b : R=Ph) complexes are kinetically controlled products that upon thermolysis led to the formation of cis-mer-[(κ²-N,S-NS₂C₇H₄)PR₃Ru{κ³-H,S,S′-H₂B(NS₂C₇H₄)₂}], (cis-mer- 2 a : R=Cy; cis-mer- 2 b : R=Ph) and cis-fac-[(κ²-N,S-NS₂C₇H₄)PR₃Ru{κ³-H,S,S′-H₂B(NS₂C₇H₄)₂}], (cis-fac- 3 a : R=Cy; cis-fac- 3 b : R=Ph) along with complex cis-[(κ²-N,S-NS₂C₇H₄)₂Ru(PPh₃)₂], (cis- 4 ). One of the main intentions of this study was to examine the flexibility of the borate and hemilabile N,S-chelating mercapto-benzothiazole ligands in adapting different spatial arrangements around metal center. Multinuclear spectroscopic analyses have been done to characterize all new complexes and the structures were further confirmed by single-crystal X-ray diffraction analysis. Further, Density Functional Theory (DFT) calculations were performed to provide an insight into the bonding of the complexes.     

Structure and Properties of a New Rare-earth Borate LiSrY_2（BO_3）_3

The structure of LiSrY2(BO3)3 has been solved by single-crystal X-ray diffraction analysis at 298 and 113 K on different diffractometers.It crystallizes in trigonal with space group P-3m1(No.164).The cell parameters at room temperature are as follows:a = 10.3345(9),c = 6.4049(11) ,V = 592.41(13) 3,Z = 3,Mr = 448.81,F(000) = 618,μ = 21.327 mm-1 and Dc = 3.774 g/cm3.The crystal structure consists of gear-like [BY6O33] groups which are linked together by corner-sharing to form a two-dimensional layer parallel to the ab plane.These layers are connected one after another by sharing oxygen atoms with B(2) atoms along the c direction to construct a three-dimensional framework.Li and Sr atoms just occupy the cavities formed by oxygen atoms.In addition,the vibrational spectroscopy of LiSrY2(BO3)3 and photoluminescence properties of the Eu3+ doped LiSrY2(BO3)3 were also studied.     

An Alcohol-templated Borate Based on [B14O20（OH）6]4- Polyborate Anions

A new borate [H2EG][B7O10（OH）3] （1） based on [B14O20（OH）6]4- polyborate anions has been solvothermally synthesized in the presence of H2EG as a template （EG = ethylene glycol）. The structure was determined by single-crystal X-ray diffraction and further characterized by FFIR, elemental analysis and thermogravimetric analysis. Compound 1 crystallizes in the triclinic system, space group Pi, with a = 8.5095（4）, b = 8.8694（4）, c = 10.0756（4） A, a = 95.094（2）, β = 96.936（2）, γ = 116.844（2）°, V = 664.66（5） A3. The structure of 1 consists of [B14O20（OH）6]4- moiety, which could be regarded as the largest isolated polyborate anion so far. The anions are interlinked via hydrogen bonding to form a 3D supramolecular network, whereas the diprotonated [H2EG]2＋ are filled in the free space of inorganic borate network and interact with the inorganic framework by extensive hydrogen bonds. It is noteworthy that the EG acts not only as a solvent, but also as a template.     

Access to Bis(σ-B−H) Complexes of Ruthenium Bearing Monoaryl Borate and Borane Ligands

A series of ruthenium bis(σ-B−H) borate complexes 1 – 4 have been prepared by a salt-elimination protocol using lithium monoaryl trihydroborates Li[ArBH₃] (R=Ph, 3,5-(CF₃)₂C₆H₃, o-tol or Mes) and the corresponding metal halide Cp*Ru(PCy₃)Cl. All of these bis(σ-B−H) borate complexes are stable at room temperature and isolated in good yields (70–92 %). Additionally, treatment of 4 with the hydride abstracting agent B(C₆F₅)₃ generated rare cationic bis(σ-B−H) borane complex 5 . Crystallographic characterization data are provided for 3 and 5 . All these new complexes were fully characterized by multinuclear NMR spectroscopy and elemental analysis.     

Comparison of Functional Group Selective Ion–Molecule Reactions of Trimethyl Borate in Different Ion Trap Mass Spectrometers

We report here a comparison of the use of diagnostic ion–molecule reactions for the identification of oxygen-containing functional groups in Fourier-transform ion cyclotron resonance (FTICR) and linear quadrupole ion trap (LQIT) mass spectrometers. The ultimate goal of this research is to be able to identify functionalities in previously unknown analytes by using many different types of mass spectrometers. Previous work has focused on the reactions of various boron reagents with protonated oxygen-containing analytes in FTICR mass spectrometers. By using a LQIT modified to allow the introduction of neutral reagents into the helium buffer gas, this methodology has been successfully implemented to this type of an ion trap instrument. The products obtained from the reactions of trimethyl borate (TMB) with various protonated analytes are compared for the two instruments. Finally, the ability to integrate these reactions into LC-MS experiments on the LQIT is demonstrated.     

Synthesis and Crystal Structure of a Rubidium Lanthanum Borate Rb3La3（BO3）4

The title compound was obtained by the flux method and its structure was determined. It crystallizes in monoclinic, space group P2/c with a = 11.0024（17）, b = 9.2979（14）, c = 14.500（2） A, β = 110.879（2）°, V = 1385.9（4） A^3, Z = 4, Mr= 908.38, F（000） = 1592, p = 19.601 mm^-1, Dc = 4.353 g/cm^3, the final R = 0.0481 and wR = 0.1257 for 2532 observed reflections with I 〉 2σ（I）, The Rb3La3（BO3）4 structure can be viewed as a 3-dimensional scaffold-like framework constructed by La-O polyhedra and BO3 groups. Two Rb＋ ions locate in a channel along the a direction and the rest one in a cavity.     

Syntheses, Structural Characterization of Fe and Ni Complexes with Polypyrazolyl Borate Ligand ： Fe [ HB （pz） 3 ] 2 and Ni [ HB （pz） 3 ] 2

Fe(Ⅱ) complex Fe[HB(pz)3]2(compound 1, pz=pyrazole) and Ni(Ⅱ) complex Ni[HB(pz)3]2(compound 2) have been obtained by the reaction of MCI2(M=Fe and Ni) with NaHB(pz)3 in MeOH. The two complexes(compounds 1 and 2) were characterized by IR, NMR, elemental analysis and X-ray diffraction. Compound 1 crystallizes in space group P21/c with a=1.224(3) nm, b=1.161(2) nm, c=1.648(3) nm, β=107.62(15)°, V=2.233(8) nm3, Z=2. Compound 2 crystallizes in space group P21/c with a=0.97926(18) nm, b=1.7423(3) nm, c=1.3156(2) nm, β=97.055(16)°, V=2.2277(7) nm3, Z=4. The results of X-ray structural analyses show that both compounds 1 and 2 are monomeric neutral, possessing a similar coordination mode and a similar structure around the metal centers. The related spectral characterizations, steric effects and binding properties are discussed.     

K2Na3[{B6O10(OH)}{B3O4(OH)3}] ⋅ H2O: A Layered Borate Built by Mixed Oxoboron Clusters with Nonlinear-Optical Property

A new acentric borate, K₂Na₃[{B₆O₁₀(OH)}-{B₃O₄(OH)₃}] ⋅ H₂O ( 1 ) has been made under solvothermal condition. 1 has layered structure made by B₆O₁₃(OH)-based chains and B₃O₅(OH)₃-bridging clusters. Second-harmonic generation (SHG) measurements reveal that 1 is a phase-matchable nonlinear optical (NLO) material, showing the SHG signal intensity of 1.8 times that of KDP (KH₂PO₄). Besides, UV-Vis diffuse reflectance spectrum shows that 1 has the short deep UV (DUV) absorption cutoff edge of 198 nm. Thermogravimetric analysis reveals it has good thermal stability. Also 1 represents firstly mixed oxoboron clusters-made 2D layered borate with NLO property.     

Synthesis and Structural Characterization of a New Polyoxovanadium Borate: (H3NCH2CH2NH3)4[(VO)6(B10O22)2]·(H3O)7

The title compound (H3NCH2CH2NH3)4[(VO)6(B10O22)2](H3O)7 1 has been synthe- sized by the hydrothermal method and determined by X-ray crystallography.Crystallographic data: monoclinic, space group C2/c, a = 20.250(4), b = 13.448(3), c = 21.655(4) (A), β = 97.05(3)°, Mr = 851.74 (C4H30.5B10N4O28.5V3), V = 5852(2) (A)3, Z = 8, Dc = 1.933 g/cm3, μ = 1.057 mm-1, F(000) = 3436, R = 0.0500 and wR = 0.1442 for 4511 observed reflections with I > 2δ(I).The structure con- sists of [(VO)6(B10O22)2]15- cluster anions that have a central band of six trans-edge-sharing VO5 square pyramids capped by two [B10O22]14- polyborate ligands.Other characterizations are also describ- ed by elemental analysis, IR spectrum and thermal analysis.     

Synthesis and Structural Characterization of a New Polyoxovanadium Borate: (H_3NCH_2CH_2NH_3)_4[(VO)_6(B_(10)O_(22))_2]·(H_3O)_7

1 INTRODUCTION Transition metal oxide clusters and their deriva- tives offer an unmatched variety of structural motifs and wide ranging applications in several areas, such as analytical chemistry, materials science and cataly- sis, nanotechnology, chemical sensing, environmental decontamination, biochemical and geochemical pro- cesses, and medicine[1～3]. Polyoxovanadates or vana- dium oxide clusters constitute an important subclass of polyoxometalates and have been studied exten- sively.…     

Synthesis and crystal structure of [Et<Subscript>4</Subscript>N] [Cr(PzTp)Cl<Subscript>3</Subscript>] [PzTp<Superscript>−</Superscript> = Tetra(pyrazolyl) Borate]

Treatment of CrCl₃(THF)₃ with KPzTp in THF affords of the compound K[Cr(PzTp)Cl₃], and the K⁺ in this complex can be replaced by Et₄N⁺ in CH₂Cl₂. Well-defined green crystals of [Et₄N]r(PzTp)Cl₃] (I) suitable for X-ray diffraction are obtained at −₂0°C. In the anion the metal center shows a distorted octahedral geometry with the tetra(pyrazolyl) borate bonded as three N-donor tripod ligands and three chloride atoms completing the coordination sphere.