Se(Ⅳ)-I^--L(L=RhB,MG,MV,CV)三元配合物的合成与表征

在室温水溶液体系中分别合成了Se(Ⅳ)-I--罗丹明B、Se(Ⅳ)-I--孔雀绿、Se(Ⅳ)-I--甲基紫、Se(Ⅳ)-I--结晶紫4种三元配合物,并用等离子体原子发射光谱(ICP)、元素分析(EA)、红外光谱(IR)、紫外可见光谱(UV-Vis)、X射线衍射(XRD)等对其进行表征,确定了4种配合物的分子式为:(RhB)2(SeI6)、(MG)2(SeI6)、(MV)4(SeI8)、(CV)4(SeI8),初步探讨了配合物的作用机理.

氯化镝与α-丙氨酸配合物的合成及表征

合成了氯化铜与α－丙氨酸的两种配合物：Ｄｙ（Ａｌａ）Ｃｌ３·６Ｈ２Ｏ和Ｄｙ（Ａｌａ）Ｃｌ３·３Ｈ２Ｏ。用化学分析，ＩＲ，ＤＶ，Ｘ－射线及ＴＧ—ＤＴＧ对配合物进行了表征。

2,4-二羟基二苯甲酮合镍(Ⅱ)配合物的合成及热分解动力学研究

合成了一种新的镍(Ⅱ)配合物Ni(C13H9O3)2.2H2O,并用元素分析I、R、UV和摩尔电导分析等手段对配合物进行了表征,用热重-差热法(TG-DTG)研究了配合物的热分解动力学,得到第二步的动力学方程。结果表明,配体中羰基氧、邻位羟基氧与金属离子配位,金属离子与配体的化学计量比为1∶2。配合物在动态空气气氛中第二步热分解由机理函数f(α)=1-α控制,反应速率方程为:dα/dt=5.295×109[exp(-105.61×103)/RT]×(1-α)。

Synthesis and Structural Characterization of [Mn(phen)_2(H_2O)_2](OAc)_26H_2O

The title complex [Mn(phen)2(H2O)2](OAc)26H2O (phen = 1,10-phenanthroline, C12H8N2, OAc = acetate, C2H3O2) with formula C28H38MnN4O12 and Mr = 677.56 has been syn- thesized and structurally characterized by X-ray diffraction. The crystal is of triclinic, space group P ?with a = 9.6201(5), b = 13.4663(7), c = 14.5375(8) , a = 108.428(1), b =93.898(1), g = 110.492(1), V = 1639.5(2) ?, Dc = 1.373 g/cm3, F(000) = 710, = 0.468 cm-1 and Z = 2. The final refinement gave R = 0.0522 and wR = 0.1259 for 4714 observed reflections with I > 2s(I). It consists of discrete [Mn(phen)2(H2O)2]2+ cation, two acetate anions and six lattice water molecules. The MnII ion coordinated by four nitrogen atoms from two chelating phen and two oxygen atoms from two cis-related water molecules is in a distorted octahedral coordination environment. Two OAc- anions and six water molecules exist outside the [Mn(phen)2(H2O)2]2+ cation as counter ions and solvate molecules, respectively. The cations and anions are interconnected by the solvate water molecules which are hydrogen bonded to both aqua ligands and acetate oxygen atoms, building up the crystals of this compound to be a supramolecule-like aggregate.

Synthesis and Crystal Structure of cis-[1,2-Bis(phenyl-thiomethyl)benzene]dichloroplatinum(Ⅱ)·0.5acetonitrile

The title complex was prepared from the reaction of 1,2-bis(phenylthiomethyl)- benzene L with K2PtCl4 at room temperature and its structure has been determined by single-crystal X-ray diffraction. There exist two independent cis-[1,2-bis(phenylthiomethyl)benzene]dichloro- platinum(Ⅱ) [PtCl2L] molecules without significant structural difference and a molecule of acetonitrile in one crystallographic asymmetric unit. Crystallographic data: triclinic, space group Pī, a = 11.010(3), b = 12.080(3), c = 16.095(4) ? = 94.728(5), = 90.129(5), = 99.274(5)? C20H18Cl2NPtS20.5CH3CN, Mr = 608.98, V = 2105(1) ?, Z = 4, Dc = 1.921 g/cm3, (Mo-K) = 7.122 mm1, F(000) = 1172, R = 0.0503 and wR = 0.0848 for 3929 observed reflections with I > 2s(I). The title complex is a neutral molecule in which the central Pt(Ⅱ) ion is four-coordinated with two S-donors of the ligand and two Cl anions, forming a distorted square planar geometry. In the crystal, there exist two kinds of molecular packing patterns. One [PtCl2L] molecule is connected to the other one through the weak interactions of Pt…Pt, Pt…S and Pt…Cl, forming a supramolecular quasi-dimer. The other one complex molecule is connected with the CH3CN molecule by weak Cl…N interaction.

Synthesis and Characterization of Rh-Co Butterfly Clusters Capped by Functionally Substituted 1-Alkynes

By the reactions of [Rh2Co2(CO)12] 1 with functionally substituted alkyne ligands HC≡CR 2 (R = FeCp2) and 3 (R = 2-OH-C6H4COOCH2), respectively in n-hexane at room temperature, two new cluster derivatives [Rh2Co2(CO)6(-CO)4(4, 2-HC≡CR)] 4 (R = FeCp2) and 5 (R = 2-OH-C6H4COOCH2) were obtained respectively. The alkyne was inserted into the CoCo bond of cluster 1 to give two butterfly clusters. Cluster 4 has been determined by single-crystal X-ray diffraction. Crystallographic data: C22H10Co2FeO10Rh2, Mr = 813.83, orthorhombic, space group P212121, a = 11.5318(7), b = 12.6572(7), c = 17.018(1) ? V = 2483.9(3) 3, Z = 4, Dc = 2.176 g/cm3, F(000) = 1568, = 3.233 mm-1, the final R = 0.0366 and wR = 0.0899 for 5367 observed reflections with I > 2(I). The two clusters have also been characterized by elemental analysis, IR and 1H-NMR spectroscopy.

Synthesis and Structural Characterization of Pd[CH_3O(O)C_6H_3CHNNC(S)NH_2](C_5H_5N)

The reaction of palladium chloride with isovanillin semithiocarbazone (VSTC), CH3O(OH)C6H3CH=NNC(S)NH2, in a mixed solvent of ethanol, pyridine and water yielded the mononuclear palladium(Ⅱ) complex Pd[CH3O(O)C6H3CHNNC(S)NH2](C5H5N), and its single- crystal structure was determined by X-ray diffraction. The crystal belongs to triclinic, space group P with a = 7.715(4), b = 9.809(6), c = 10.612(4) ? a = 93.54(4), b = 111.00(3), g = 95.92(5), V = 745.0(7) 3, Mr = 408.75, Z = 2, Dc = 1.822 g/cm3, m = 1.397 mm-1, and F(000) = 408. The final R = 0.0568 and wR = 0.1439 for 2616 observed independent reflections with I ≥ 2.0s(I). It was revealed that the palladium atom is bound to a tridentate donor ligand and a pyridine in a planar square arrangement. The sulphur-nitrogen-oxygen donor of the Schiff-base ligand in the thiol form rather than the thione one is coordinated to the palladium atom via the mercapto sulphur, the b-nitrogen and the hydroxylate oxygen atoms.

Synthesis and Characterization of Dimeric Copper（ll） and Nickel（ll） Complexes with Some Aroylhydrazones of a-Pyridoin and Solvent Extraction Applications

A new series of dimeric Cu（II） and Ni（II） complexes with some aroylhydrazones of a-pyridoin were synthesized and characterized using different physical techniques. Their chemical formulae were based on their microanalysis and IR data. The structures of the solid complexes were determined from the electronic, IR and ESR spectral studies as well as their magnetic susceptibility measurements. The ligands acted as bi-, tri- and tetra-dentate forming different dinuclear complexes with different structures. The assumed molecular structures based on the experimental results were also confirmed by the molecular mechanics calculations. The extraction ability of the hydrazones has been investigated by liquid-liquid extraction for Cu（II） and Ni（II）.

Synthesis and Characterization of Molybdenum（VI） Complexes with 1,10-Phenanthroline

The development of routes and strategies for the design and preparation of complexes of 4d metals in moderate oxidation states is of great importance in magnetochemistry, bioinorganic chemistry, materials chemistry and solid-state chemistry. Bidentate ligands containing N or O donors especially phenanthroline have been widely used to form complexes with interesting structural motif. Reaction of M（CO）6 （M = Cr, Mo, W） with phenanthroline has been done in 1935 and produced an interesting stereo structure, but the reaction of MoOE（acac）2 （acac = acetylacetonato） with phenanthroline has not been studied yet. So, in this research, first of all MoOE（acac） 2 was prepared, and then it reacted with bidentate nitrogen donor to lead to produce the complex of [MoOEL2] （L = Phen） and different aspects of this complex were studied. This complex is very active and highly selective epoxidation catalyst. The structure of the product was characterized by various spectral techniques such as elemental analysis, IH NMR, 13C NMR and IR spectroscopy.

Synthesizes and Characterization Studies of Some Metal Ion Complexes with EOSBE and MOSBE

This work includes synthesis of 2,2＇-（5,5＇-（ethane-1,2-diyl）bis（1,3,4-oxadiazole-5,2diyl））bis（sulfanediyl）dibenzenamine （EOSBE） and 2,2＇-（5,5＇-methylenebis（1,3,4-oxadiazole-5,2-diyl）bis（sulfanediyl））dibenzenamine （MOSBE）. All synthesized ligands were characterized by IR, ^1H-NMR, ^13C-NMR, UV-visible spectroscopies and molar conductivity. A series of complexes with a general formula [M2LCl4]. Where M（Ⅱ） = Co, Ni, Cu and Zn; L = EOSBE and MOSBE were synthesized in basic media using KOH solution. In these complexes both ligands are bidentate ligands coordinated through sulfur and nitrogen. All complexes have been characterized by IR-spectra, UV-visiblc spectra, conductivity and magnetic susceptibility.

Syntheses of Two Chiral Clusters [η~5-C_5H_4C(NR)CH_3]- RuNiM(CO)_5(μ_3-S) (R =NH-C_6H_3-2,4-(NO_2)_2,M=Mo,3;M=W,4) and the Single-crystal Structure of Cluster 3

The new chiral clusters [h5-C5H4C(NR)CH3]RuNiM(CO)5(m3-S) (R = NH-C6H3-2,4- (NO2)2, M = Mo, 3; M = W, 4) were synthesized and the structure of cluster 3 was determined by single-crystal X-ray analysis. Crystal data: C23H16O9N4MoNiRuS, Mr = 780.18, orthorhombic, space group Pbca with the following crystallographic parameters: a = 13.207(4), b = 16.036(5), c = 25.513(8) , Z = 8, V = 5403(3) 3, Dc = 1.918 g/cm3, m = 1.834 mm-1 and F(000) = 3072. The final R = 0.0512 and wR = 0.1132 for 2525 reflections with I > 2.00s(I).

Synthesis and Crystal Structure of a New Chain Coordination Polymer [Cu(inio)_2(H_2O)]_∞(Inio = Isonicotinic Acid N-Oxide)

A new Cu(Ⅱ) coordination polymer [Cu(inio)2(H2O)] (inio = isonicotinic acid N-oxide) with chemical formula C12H10CuN2O7 was prepared and its crystal structure has been determined by X-ray analysis. The complex crystallizes in the monoclinic system, space group C2/c with a = 12.455(3), b = 6.202(1), c = 16.555(3) ? b = 106.776(3), V = 1224.3(4) 3, Z = 4, Mr = 357.76, Dc =1.941 g/cm3, m(MoKa) = 1.827 mm-1, F(000) = 724, R = 0.0601 and wR = 0.1417 for 908 observed reflections (I > 2s(I)). The Cu(Ⅱ) atom is coordinated by an elongated square pyramid geometry. The deprotonated isonicotinic acid N-oxides form a double-bridge between each pair of Cu(Ⅱ) ions in trans form through two oxygen atoms from the carboxyl groups and two other oxygen atoms from the -NO groups, respectively, which leads to an infinite one dimensional chain. The two adjacent elongated Cu(Ⅱ) square pyramidal geometries are arranged in trans form in the same chain. The OH…O hydrogen bonds extend the chain structure into two-dimensional layers.

Synthesis and characterization of a tetradentate PNCP iridium complex for catalytic alkane dehydrogenation

A novel hydrido iridium chloride complex supported by a tetradentate PNCP ligand has been synthesized and characterized. Upon activation with NaOtBu, the PNCP-IrHC1 complex is active for transfer dehydrogenation of cyclic and linear alkanes.

Synthesis and characterization of MH···HOR dihydrogen bonded ruthenium and osmium complexes（η~5-C_5H_4CH_2OH）MH（PPh_3）_2（M = Ru, Os）

Treatment of RuCl2(PPh3)3 with 6-dimethylaminopentafulvene in THF in the presence of water produced(η5-C5H4CHO) RuCl(PPh3)2, which was reduced by NaBH4 to give the Ru–H···HO dihydrogen bonded complex(η5-C5H4CH2OH) RuH(PPh3)2. The dihydrogen bonded complex(η5-C5H4CH2OH)RuH(PPh3)2 could also be synthesized by the reduction of complex(η5-C5H4CHO)RuH(PPh3)2, which was obtained by the reaction of RuHCl(PPh3)3 with 6-dimethylaminopentafulvene in the presence of water. The analogous dihydrogen bonded osmium complex(η5-C5H4CH2OH)OsH(PPh3)2 was similarly prepared. Single crystal structures and DFT calculations support the presence of intra-molecular H···H interaction, with separations of around 1.9 to 2.0 .