Chlorine-Induced Hydrogen-Bonding Network of A Novel Dimer Based on Nickel and Tridentate Ligand： 3-Hydrazine-4-amino-1,2,4-Triazole

The reaction of NiCl2 and 3-hydrazine-4-amino-1,2,4-triazole （Hatr） in the mixed solvent of EtOH and H2O yielded a dimer compound （[Ni2（Hatr）2（H2O）2（EtOH）2Cl2]ClzoEtOH） with water and EtOH molecules coordinated to nickle ions. It crystallized in trigonal space group R-3, a=b=29.67（1） A, c=8.95（7） A, β= 120（1）°, as determined by single-crystal X-ray diffraction. Then, they were fully characterized by the IR spectroscopy, differential scanning calorimetry （DSC）, thermogravimetry （TG）, and elemental analysis.

Coordination chemistry of organometallic polydentate ligand Reactive chemistry of the tridentate ligand trans-Fe(Ph_2PQu-P)_2- (CO)_3 [Ph_2PQu=2-diphenyl-phosphino-4-methylquinoline] and molecular structure of [Fe(CO)_3(μ-Ph_2PQu)_2HgI]^+[HgI_3]

Reaction of a new type of bidentate ligand PhPQu [ PhPQu = 2-diphenylphosphino-4-methylquinoline] with Fe(CO)5 in bu-tanol gave trans-Fe(PhPQu-P)(CO)3 (1).Compound 1,which can act as a neutral tridentate organometallic ligand,was reacted with I B,II B metal compounds and a rhodium complex to give six binuclear complexes with Fe-M bonds,Fe(CO)3(u-Ph2PQu)MXn(2-7) [M=Zn(Ⅰ),Cd(Ⅱ),Hg(Ⅱ),Cu(Ⅰ),Ag(Ⅰ),Rh(Ⅰ)],and an ion-pair complex [Fe(CO)3(n-Ph2PQu)2HgI][HgI3]- (8).The structure of 8 was determined by X-ray crystallography.Complex 8 crystallizes in the space group P-1 with a=1.0758(3),b= 1.6210(4),c = 1.7155(4) nm; a = 75.60(2)β=71.81(2),Y = 81.78(2) and Z = 2 and its structure was refined to give agreement factors of R =0.050 and Rw = 0.057.The Fe-Hg bond distance is 0.2536 nm.

Chiral Phenol-2NO Ligand Cooperation with Achiral Organic Base in the Zn(II)-Catalyzed Asymmetric Alkylation Reaction of Indoles

The privileged C_(2)-symmetric rigid phenol-type ligand is more attractive but challenging in asymmetric catalysis.Herein,we designed and synthesized a class of rigid-featured chiral tridentate Phenol-2NO ligands,that incorporate the advantages of both the phenol skeleton and pyrroloimidazolone-based N-oxide moiety,from readily available L-prolinamides in operationally simple two steps and up to 44%overall yield.More importantly,using an achiral quinoline derivative as an additive,the newly developed Phenol-2NO ligand could serve as the anioic ligand upon deprotonative activation to coordinate to Zn(II)to form a highly enantioselective catalyst for the asymmetric Michael-type Friedel-Crafts alkylation reaction of indoles with 2,3-dioxopyrrolidines.Excellent yields(up to 90%)and high enantioselectivities(up to 99%ee)are obtained for a wide range of substrates under mild conditions.Experiments and DFT calculations revealed the reaction mechanism and the origins of the enantioselectivity.This also represented the first activation of phenol-type ligand/metal complex by an achiral organic base as the additive in asymmetric catalysis.

Probing the dynamic thermodynamic resolution and biological activity of Cu(Ⅱ) and Pd(Ⅱ) complexes with Schiff base ligand derived from proline

Schiff base metal complexes are of great importance in pharmaceutical science owing to their unique chemical properties, which enable them to exhibit diverse biological activities such as anti-bacterial,anti-oxidant, anti-inflammatory, and anti-tumor properties. Furthermore, Schiff base metal complexes can serve as reagents and catalysts in chemical reactions. This review aims to provide an overview of our recently published studies on Cu(Ⅱ) and Pd(Ⅱ) complexes derived from proline Schiff base ligands. We also discuss the potential applications of these metal complexes in the fields of antibacterial and chiral resolution.

Synthesis and Crystal Structure of a Vanadium(V) Complex with 2-Hydroxy-1-naphthaldehyde Isonicotinoyl Hydrazone

The mononuclear vanadium（V） complex with 2-hydroxyl-l-naphthaldehyde isonicotinoyl hydrazone was synthesized and characterized by single-crystal X-ray diffraction. The crystal is of monocfinic, space group P2 1/n with α = 10.3153（15）, b = 7.4024（11 ）, c = 24.413（4） A, β = 101.911（2）°, V= 1824.0（5） A^3, Z= 4, Mr = 427.28, Dc = 1.556 g/cm^3, F（000） = 880,μ（MoKα） = 0.591, the final R = 0.0372 and wR = 0.0926. The vanadium（V） atom adopts a distorted square-pyramidal geometry coordinated by the tridentate ligand and two oxygen atoms. The hydrogen bonds and strong π-π stacking interactions link the complex molecules into a 3-D network structure.

Activation of Nitromethane to Cyanide by a Mononuclear Cu(Ⅱ) Complex

The tridentate ligand DPA-Me（2） was readily prepared from DPA（DPA = 2,2-dipicolylamine） in high yield. The mixture of 2 and Cu（ClO4）26H2O in methanol gave a five-coordinated mononuclear complex [（DPA-Me）Cu（Me CN）（ClO4）]（ClO4）（3）. Recrystallization of 3 in CH3NO2 led to an activation of CH3NO2 to CN- by the formation of product as a dinuclear cyanide bridged complex {[Cu（DPA-Me）]2（CN）（ClO4）3CH3NO2}n（4）. Both 3 and 4 were characterized by X-ray crystallography, IR spectroscopy and elemental analysis. The crystal of 4 was grown in space group P21/c with a = 17.74582（15）, b = 13.89877（11）, c = 14.92546（13） A, β = 91.4246（8）°, V = 3680.15（5） 3, Z = 4, Dc = 1.695 g/cm^3, F（000） = 1912, C28H33Cl3Cu2N8O14, Mr = 939.05, μ = 1.602 cm^-1, Cu Kα radiation（λ = 1.54184 ）, R = 0.0485 and w R = 0.1246 for 6414 observed reflections with I 〉 2σ（I）.

SYNTHESES,CHARACTERIZATION AND ETHYLENE POLYMERIZATION OF HALF-SANDWICH GROUP IV METAL COMPLEXES WITH TRIDENTATE [O,N,S] LIGANDS

A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N = CHC6H2O）]- （La） and dianionic phenoxy-amine arylsulfide [O-N-S] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N-CH2C6H2O）]2- （Lb） have been synthesized and characterized. Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH4 in cool diethyl ether. Half-sandwich Group Ⅳ metal complexes CpTi[O-NS]Cl2 （1a）, CpZr[O-NS]Cl2 （1b）, CpTi[O-N-S]Cl （2a）, CpZr[O-N-S]Cl （2b） and CpZr[O-N-S]Cl （2c） were synthesized by the reactions of La and Lb with CpTiCl3, CpZrCl3 and Cp ZrCl3, and characterized by IR, ^1H-NMR, ^13C-NMR and elemental analysis. In addition, an X-ray structure analysis was performed on ligand Lb. The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane （MAO） as co-catalyst up to 1.58 × 10^7 g-PE.mol-Zr-1.h-1. The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.

Synthesis and Crystal Structure of 2-Benzoyl Pyridine Thiosemicarbazato Palladium(Ⅱ)Chloride

The title complex, 2 benzoyl pyridine thiosemicarbazato palladium(II) chloride [C 13 H 11 N 4SPdCl, M r =379.17], crystallizes in monoclinic, space group C2/c with a=12.1061(5), b=21.877(3), c=11.4832(6), β=108.29(9)°, V=2887.7(4) 3, Z = 8, D c =1.827g/cm 3; μ= 1.608cm -1 and F(000)=1568. R =0.0281 and wR =0.0684 for 1446 reflections with I>2σ(I) . X ray crystal structure analysis revealed that the coordination geometry of Pd atom is a distorted square plane with two Pd-N bonds, one Pd-S bond and one Pd-Cl bond. The Schiff base ligand loses a proton from its tautomeric thiol form and coordinates to the Pd atom via the mercapto sulfur and the β nitrogen atoms.

Isospecific Polymerization of Methyl Methacrylate by Intramolecular Rare-Earth Metal Based Lewis Pairs

A series of cationic rare-earth aryloxide complexes,ie,,[LREOAr^(1)]^(+)[B(C_(6)F_(5))_(4)]^(-)(L=CH_(3)C(NAr)CHC(CH_(3))(NCH(R)CH_(2)PPh_(2));RE=Y,Lu;Ar'=2,6-tBU_(2)-C_(6)H_(3),2,6-(PhCMe_(2))_(2)-4-Me-C_(6)H_(2);Ar=2,6-iPr_(2)-C_(6)H_(3),2,6-(Ph_(2)CH)_(2)-4-iPr-C_(6)H_(2);R=H,CH_(3),iPr,Ph),were prepared and ap-plied to the Lewis pair polymerization of methyl methacrylate(MMA).The stereoregularity of the resulting PMMA was significantly affected by the R substituent on the pendant arm of the tridentate NNP ligand,and was found to increase with increase in the steric hindrance of R.

A One-Pot Strategy for the Synthesis of β-Substituted Rhoda-and Irida-Carbolong Complexes

Comprehensive Summary Starting from an organic multiyne,three steps are normally needed for the preparation of non-βphosphonium functionalized rhodaand irida-carbolong complexes.Herein,a one-pot strategy,by mixing a multiyne,a nucleophile,and Rhcl(CO)(PPh_(3))_(2)/AgBF_(4)or[Ir(CH:CN)(CO)(PPh_(3))_(2)]BF_(4),was developed to achieve a series ofβfunctionalized rhoda-and irida-carbolong complexes.Theβ-substituents in these complexes can be various C-,N-and O-centered groups,dependent on the nucleophiles used.This strategy provides a new convenient route to construct carbolong complexes,which is important for the further development of carbolong chemistry.

Copper-catalyzed asymmetric propargylic substitution of anthrones and propargylic esters

Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Herein, we disclosed a highly enantioselective propargylic substitution of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand. This strategy is amenable to a broad range of substrates, uses readily available starting materials, provides excellent yields with remarkable enantioselectivity under mild conditions, and enables attractive products diversification routes.