A novel ionic iridium complex was synthesized under mild condition with 2,4-difluorophenylboronicacid, 2-chloroquinoline. The complex was characterized by elemental analysis, IR, 1 H-NMR, MS(ESI) and X-ray diffraction(XRD). Its light-physical properties and the thermal stability of the complex were investigated. The single crystal structure of the complex is adopting twisted octahedral coordination mode, in triclinic and space group P-1. The novel ionic iridium complex produces a strong photoluminescence at 542 nm and CIEx, y coordinates of (0.41, 0.57).

Two bipyridine derivatives(L1,L2) were synthesized from 4,4′-dibromo-2,2′-bipyridine, 3,5-dimethylbenzeneboronic acid and 2,4-difluorophenylboronic acid. A chloride-bridgeed dimer [ Ir (mqu)2(μ-Cl2)]2 was prepared by reaction of IrCl3 with 2-(3,5-dimethylphenyl)quinoline which was synthesized from 2-chloroquinoline and 3,5-dimethylbenzeneboronic. Two novel ionic iridium comple-xes(Ir-1 and Ir-2), with 2-(3,5-dimethylphenyl)quinoline as primary ligand, L1 and L2 as N^N an-cillary ligands, were obtained. The structures were characterized by 1 H NMR, IR, MS( ESI) and ele-mental analysis. The light-physical properties and thermostability of the complexes were investigated. The results showed that Ir-1 and Ir-2 produced a strong photoluminescence at 591 and 623 nm, and CIE coordinates of (0. 58, 0. 42) and (0. 61, 0. 39), respectively. The complexes exhibited good performance in thermostability with the decomposition temperature up to 339 ℃ for Ir-1 and 340 ℃ for Ir-2, respectively.

通过在2,4二氯吡啶上引入3-联苯基,合成了一种以2,4-二(3-联苯)吡啶为主配体,以2,2,6,6-四甲基-3,5-庚二酮为辅助配体的新型有机电致磷光材料,通过元素分析、红外光谱、1H NMR和质谱对产物进行了结构表征,利用X射线单晶衍射仪测定了配合物的晶体结构.并对其用紫外-可见吸收、光致发光、热稳定性等进行研究.研究表明,配合物在395和465 nm处存在单重态1 MLCT(金属到配体的电荷跃迁)和三重态3 MLCT的吸收峰;其初始分解温度为405℃(对应于10％质量损失),最大发射波长为570nm,是一种可用于白色有机电致发光器件的新型黄色发光磷光材料.

以氯桥二聚体(ppy)2 Ir(μ-Cl2)Ir(ppy)2、4,4'-二溴-2,2'-联吡啶和六氟磷酸钠为原料合成了一种新型离子型铱配合物[Ir(ppy)2 (Br2bpy)]+PF6,产率90％.采用元素分析、红外光谱、核磁谱以及质谱表征确认了目标产物的结构,并考察了其光物理性能.结果 发现,配合物[Ir (ppy)2(Br2 bpy)]+PF6-在630 nm处具有很强的红光发射光谱.并采用溶剂缓慢挥发法培养出[Ir(ppy)2 (Br2bpy)]+PF6-的单晶,X射线单晶衍射仪对其结构进行了表征,获得了晶体结构参数,结果表明配合物为正交晶系,P212121空间群.

以卤化钯(X=Cl、Br、I)为原料,乙腈为溶剂,与1,2-二(二苯基膦)乙烷反应,合成了1,2-二(二苯基膦)乙烷卤化钯[Pd(dppe)X2,dppe=1,2-二(二苯基膦)乙烷],产率均高于96％,其结构经1H NMR,XRD和元素分析确证.以Suzuki反应和Stille C—C偶联反应为模板反应,研究了Pd(dppe)Cl2的催化活性.结果表明:Pd(dppe)Cl2对2-氯噻吩和对甲氧基苯硼酸的Suzuki偶联反应、4,7-二氯苯并噻二唑核或其他含苯并噻二唑核的卤代芳烃与其他芳香核的锡试剂的Stille C—C偶联反应的催化转化率分别为80％～85％和52％～60％,催化活性优于四(三苯基膦)钯(70％～85％和43％～50％).

A new cyclometalated ruthenium complex was synthesized from 2,4-difluorobenzeneboronic acid, 4,4'-dibromo-2,2'-bipyridine and cis-bis-(2,2'-bipyridine)dichlororuthenium(II) dehydrate. The complex was characterized by element analysis, IR spectra,1H-NMR and mass spectrometry. Its UV-Vis absorption and photoluminescence was measured. The data showed that an introduction of the 2,4-difluoro-phenyl substituent into the 4,4'-site of 2,2'-bipyridine would alter metal-to-ligand charge transfer (MLCT) transition, leading to a significant red shift of the photoluminescence spectra (λmax) from 590 to 613 nm. The cyclometalated ruthenium complex, as evidenced by TG measurements, has good thermo- stability and the decomposition temperature is up to 356℃.

Chiral 2,2'-bis(diphenylphosphino)-1,1'-binapthyl (Binap) ligand consists of a pair of 2-diphenylphosphinonaphthyl groups connected at the 1 and 1' positions, being of the nature of the C-2-axial chirality with optical activity of +/- 234 degrees. The Binap can coordinate with many transitional metals to form stable chelation complexes, effecting the chirality transfer to the metal center for function in asymmetrically catalytic reactions. This contribution is focused on the Binap-Ru(II) catalytic system that covers the various substrates, reaction conditions, enantioselectivity of the products, reaction mechanism, and others on the basis of the prepared stable Binap-Ru(II) complexes as the clue in the text. This study will give a deep understanding of this system especially concerning the applied catalytic synthesis of the useful organic molecules.

A solid form of bis (ehanolammonium) hexahydroxoplatinate (Ⅳ) (MEA) 2Pt (OH) 6 was synthesized in a yield of 98％ from sodium hexachloroplatinate as the raw material,via hydrolysis and neutralizationdissolution.The content of platinum in the product was measured to be 46.8％ whereas both sodium and chloride ion did not exceed 200 mg/kg.The thermal decomposition reaction was investigated by means of DTA-TG,and the catalytic combustion of methane was evaluated on Pt/La-Al2O3 catalysts prepared by using (MEA)2Pt (OH) 6 as the precursor.The results imply that the compound is a good precursor for supported platinum catalysts.

The N-geminal P/Al Lewis pair [Ph2PN(2,6-iPr2C6H3)AlEt2]2 (1) has been prepared and studied for reaction with a series of alkynes. The reaction of 1 with RC≡CR yielded zwitterionic C2PNAl-heterocyclopentene [Ph2⌜PN(2,6-iPr2C6H3)AlEt2](CR=⌝CR) (R = Me (2), Ph (3)); with PhC≡CEt produced two isomers, [Ph2⌜PN(2,6-iPr2C6H3)AlEt2](CPh=⌝CEt) (4a) and [Ph2⌜PN(2,6-iPr2C6H3)AlEt2](CEt=⌝CPh) (4b); and with other alkynes generated [Ph2⌜PN(2,6-iPr2C6H3)AlEt2](CR1=⌝CR2) (R1, R2 = CO2Et, Ph (5); SiMe3, Ph (6); PPh2, Ph (7); SiMe3,H (8); H, EtO (9)). Natural bond orbital analysis of the charge separation of the C≡C bond of alkynes was carried out, and then, the electronic matching interaction mode between the combined Lewis acid (AlEt2) and base (PPh2) groups of 1 and the C≡C bond of such alkynes was discussed. Reactions of 1 with alkene, nitrile, and carbodiimide molecules were also carried out, and cycloaddition compounds 10-12 were produced.

A green but not a purple or red product was obtained by reaction of dirhodium(Ⅱ) tetraacetate with 2-picolinic acid in an aqueous solution, indicated that the 2-picolinic acid are bound to the rhodium center through O atoms but not N atoms. While the ethanol solution of the green product was allowed to evaporate slowly in the air, it was oxidized to mer-rhodium(Ⅲ) trispicolinate, which was characterized by single-crystal X-ray diffraction, by the oxygen in the air within two months. There is one molecule of water of crystallization per molecule of rhodium(Ⅲ) trispicolinate complexes. The water molecule is hydrogen-bonded to two carboxylate oxygen atoms from two adjacent rhodium(Ⅲ) trispicolinate molecules, which links the rhodium(Ⅲ) trispicolinate molecules to form a chain supramolecular structure. The chains are further packed to a three-dimensional network by the π-π interactions of the rhodium(Ⅲ) trispicolinatemolecules between the neighboring pyridine rings.

A germylene/borane Lewis pair (2) was prepared from a 1,1-carboboration of amidinato phenylethynylgermylene (1) by B(C6F5)(3). Compound 2 reacted with iPrNCO and (4-MeOC6H4)C(O)Me, respectively, with cleavage of the C=O double bond. In the first instance, O and iPrNC insert separately into the Ge-B bond to yield a GeBC2O-heterocycle (3) and a GeBC3-heterocycle (4). In the second case (4-MeOC6H4)(Me)C inserts into the Ge-N bond of 2 while O is incorporated in the Ge-B bond to form a Ge-centered spiroheterocycle (5). The reaction of 2 with tBuNC to give 6, which has almost the same structure as 4, proved the formation of the isonitrile during transformation from 2 and iPrNCO to 3 and 4. The kinetic study of the reaction of 2 and iPrNCO gave evidence of proceeding through a GeBC3O-heterocycle intermediate. In addition, a DFT study was performed to elucidate the reaction mechanism.

A new green phosphoerscent complex Ir (bppy)2pic was synthesized with 2-bromopyridine, Biphenyl-3-boronic acid and iridium trichloride anhydrate .The procedure of synthesis was simple and easy control .The complex was characterized by mass spectrometry , 1 H NMR.The UV-Vis absorption and photoluminescence of the Iridium complex were investigated.The complex showed strong single metal to ligand charge-transfer and tripletmetal to ligand charge-transfer absorption at 405 and 475 nm, respectively.The complex also produced a strong photoluminescence at 503 nm.It was suggested that the complex Ir ( bppy ) 2 pic was a new green phosphorescent material .

A new chemical technique was developed for batch synthesis of bis(2,4-difluorophenyl-pyridine-C2,N')(acetylacetonato)iridium(III), an organometallic light-emitting molecule for OLED. The process involves the reaction of a chloride-bridged dimer with acetylactone to produce the desired compound in a 10~20 gram batch scale. The yield was more than 90%, and the purity was determined by HPLC to be 99.70%. The chemical structure of the product was verified by NMR (1H and 13C) and FT-IR along with single crystal X-ray diffraction. The structural data show that Ir(dfppy)2(acac) is an electrically neutral octahedral complex. The average bond lengths of Ir-O, Ir-C and Ir-N are 0.2160(14), 0.1998(11) and 0.2030(15) nm, respectively. The iridium(Ⅲ) complex develops a strong emission band at 484 nm.

Aryl(silyl)amino group stabilized hydridosilanediols RSiH(OH)2 (R = N(SiMe2Ph)-2,6-iPr2C6H3 (), N(SiMe3)-2,6-iPr2C6H3 (), and N(SiMe2Ph)-2,4,6-Me3C6H2 ()) were prepared from the controlled hydrolysis of the related RSiHCl2 () each in the presence of aniline as the HCl acceptor. Reactions of with AlMe3, AliBu3, AlH(iBu)2, and AlH3·NMe3, respectively, yielded alumino(hydrido)siloxanes [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAlMe(THF)]2 (), [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAliBu(THF)]2 (), [2,6-iPr2C6H3N(SiMe2Ph)Si(H)O2]3[Al(THF)]2 (), and [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAlH(THF)]2 (). The reaction of with AlMe3 gave [2,6-iPr2C6H3N(SiMe3)Si(H)OAlMe(THF)]2 (), a compound similar to . Compounds are characterized by NMR ((1)H, (13)C, and (29)Si) and IR spectroscopy and CHN elemental analysis, of which and are further studied by X-ray crystallography. Compounds and feature cyclic structures all with the skeleton core of Si2O4Al2 while compound exhibits a bicyclic structure having a core of Si3O6Al2. Melting point measurements indicated that are thermally stable bearing the geminal SiH and SiOH groups. Compounds and are thermally stable as well with the O atom-bridged SiH and AlR (R = Me, iBu, or H) groups.

Rh(CO)2(acac)]2 was synthesized in one-step process from RhCl3·3H2O in DMF by adding acac as the anion ligand. The yield was 93%. A quantitative reaction between [Rh(CO)2(acac)]2 and PPh3 in n-butane gave rise to the formation of Rh(acac)(PPh3)(CO) with a yield of 99%. Single crystals of two complexes were prepared, respectively, via a gaseous diffusion method and a solvent evaporation technique, and were subjected to X-ray diffraction analysis. The results show both complexes are in the triclinic system with a space group of P-1. [Rh(CO)2(acac)]2 displays a dimmeric structure with Rh-Rh bond being 3.417 ?, whereas Rh(acac)(PPh3)(CO) has a normal mononuclear structure.

Amino group combined P/Ge-based frustrated Lewis pairs (FLPs) Ph2PN(R)GeCl3 (R = 2,6-iPr2C6H3 (1), 2,4,6-Me3C6H2 (2), and C6H11 (3)) and Ph2PN(2,6-iPr2C6H3)GeMe3 (4) as well as P/Sn-based FLP Ph2PN(2,6-iPr2C6H3)SnMe3 (5) were prepared and utilized for reactions with alkyne and aldehyde molecules. Compounds 1-3 each reacted with MeO2CC[triple bond, length as m-dash]CCO2Me to give zwitterionic cyclic vinyls [Ph2PN(R)GeCl3](MeO2CC[double bond, length as m-dash]CCO2Me) (6-8) and compound 1 reacted with HC[triple bond, length as m-dash]CCO2Me to give the similar compound [Ph2PN(2,4,6-Me3C6H2)GeCl3](HC[double bond, length as m-dash]CCO2Me) (9). Compound 4 reacted with RC[triple bond, length as m-dash]CCO2Me to afford acyclic vinyls 2,6-iPr2C6H3N[double bond, length as m-dash]P(Ph2)C(R)[double bond, length as m-dash]C(CO2Me)GeMe3 (R = CO2Me (10), H (11)) and 5 reacted with MeO2CC[triple bond, length as m-dash]CCO2Me to give 2,6-iPr2C6H3N[double bond, length as m-dash]P(Ph2)C(CO2Me)[double bond, length as m-dash]C(CO2Me)SnMe3 (12). The reactions of 1 with CH3CH2CHO and 1,4-(CHO)2C6H4 were also investigated and yielded novel zwitterionic OCPNGe five-heteroatom cycles [Ph2PN(2,6-iPr2C6H3)GeCl3][CH(CH2CH3)O] (13) and [Ph2PN(2,6-iPr2C6H3)GeCl3][p-(OCH)C6H4CHO][Cl3GeN(2,6-iPr2C6H3)PPh2] (14). Compounds 1-14 were characterized by NMR ((1)H, (13)C, and (31)P) and CHN elemental analysis, of which 1, 7, and 10-14 were further studied by X-ray crystallography. The reactions of 4 (or 5) with RC[triple bond, length as m-dash]CCO2Me to produce 10-12 present a novel way of obtaining the germyl (or stannyl) and iminophosphoranyl co-substituted vinyls.

Abstract C16H18N2O8Rh2, monoclinic, P21/c (no. 14), a = 10.635(2) Å, b = 11.375(3) Å, c = 7.854(2) Å, β = 90.634(3)°, V = 950.0 Å3, Z = 2, Rgt(F) = 0.0373, wRref(F2) = 0.0930, T = 100 K.

Three complexes were synthesized in high yields by reaction of Rh2(O2CCH3)4 with 2-picoline (1), 3-picoline (2) and 4-picoline (3), respectively, and characterized by elemental analysis, ESI+-MS, FT-IR and 1H NMR along with single-crystal X-ray structural analysis. All picoline ligands coordinate to the axial sites of Rh2(O2CCH3)4 via the pyridine nitrogen atoms, and interestingly, the coordination of 2-picoline in 1 is assisted by two intramolecular C–H⋯O hydrogen bonds formed between the methyl of 2-picoline and the oxygen atoms of Rh2(O2CCH3)4. Moreover, the intermolecular C–H⋯O interactions play the main role in the structural stacking of 1–3. Their catalytic activity was evaluated in the C–H insertion reactions for the preparation of 4-nitrobenzyl-(4R,5R,6S)-6-((R)-1-hydroxyethyl)-4-methyl-3,7-dioxo-1-azabicyclo [3.2.0] heptane-2-carboxylate, a key intermediate of Meropenem. The isolated yields for 1, 2 and 3 are 44%, 16% and 22%, respectively, significantly lower than the value of Rh2(O2CCH3)4 (73%), indicating that the axial ligands have negative but different influence on the catalytic activity. The activities of 1–3 are related to the displacement rate of the axial ligands, and essentially related to the Rh–N bond lengths which strong affect the displacement rate. Therefore, it is possible to tune the catalytic activity of Rh2(O2CCH3)4 by changing its axial ligands.

Three organic-phosphine gold(I) chlorides were synthesized from HAuCl4 as the starting chemical via a two-step process, with a yield of 95%. The reaction of HAuCl4 with dimethyl sulfide(Me2S) produced an intermediate [AuCl(Me2S)] which was then converted to the corresponding organicphosphine gold(I) chloride by mixing with triphenylphosphine(PPh3), 1,1'-bis(diphenylphosphino)-ferrocene(dppf) or 1,2-bis(diphenylphosphino)ethane(dppe). Replacing chloride in [AuCl(PPh3)] with AgSO3CF3 gave rise to the product [(CF3SO3)][Au(PPh3)].

Four new diam(m)ine platinum complexes containing the dichloroacetate moiety in 3-dichoroacetoxylcyclobutane-1,1-dicarboxylate as the leaving group were synthesized, characterized by elemental analysis as well as by ESI+-MS (electrospray ionization mass spectrometry in positive mode), FT-IR, 1H- and 13C-NMR, and evaluated for their in vitro anticancer activity against human lung cancer cell line (A549) and ovarian cancer cell lines (SK-OV-3, SK-OV-3/DDP). Diam(m)ines used in the present study belong to the carriers of six clinically approved platinum drugs. Among the complexes synthesized, complex 2, cis-[Pt(II)(1R,2R-diaminocyclohexane)·(3-dichoroacetoxylcyclobutane-1,1-dicarboxylate)] is the most promising in terms of water solubility and potential of being totally devoid of cross-drug resistance with cisplatin. Therefore, complex 2 was selected for the dichloroacetate release test. The test shows dichloroacetate can be efficiently released from complex 2 under physiological conditions via the hydrolysis of an ester bond bridging the dichloroacetate moiety and platinum pharmacophores together. Our study supports the further evaluation of this complex as a drug candidate.