Synthesis and Structure of Bis[bis(tert-butylcyclopentadienyl) Ytterbium Chloride]

1INTRODUCTIONLanthanocenechlorideisanimportantprecursorforpreparationofthecomplex-escontainingLn-CandLn-Hbonds.Allbinuclearbicyclopentadienyllanthanidechlorideswiththeunsubstitutedcyclopentadienylexceptthoseoftheearlylanthanideareavailable['3.Recently,theuseofstericallybulkyligandsorbridgedbicyclopenta-dienylhasgivenCp',LnClforearlylanthanides[2-6i.Usingt-butylcyclopentadienylasaligand,wedescribedthestructuresofcomplexes(Bu'C5H')2LnCl(THF).(Ln=Pr,Nd,n=2;Ln=Gd,Yb,n=1)t7iandtheunsol…     

SYNTHESIS AND CHARACTERIZATION OF THE SOLID COMPLEXES OF Mn(Ⅱ), Co(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Ag(Ⅰ), Cd(Ⅱ) NITRATES WITH DISUBSTITUTED BENZO CROWN ETHERS

Nine new solid complexes of Mn(Ⅱ),Co(Ⅱ),Cu(Ⅱ),Zn(Ⅱ.),Ag(Ⅰ) nitrates with 4',5'-dibromobenzo-15—crown—5(L_A),Ag(Ⅰ),Cd(Ⅱ)nitrates with tetrabromodibenzo—18—crown—6(L_B)and Cu(Ⅱ), Ag(Ⅰ) nitrates with 4'—bromo—5'—nitrobenzo—15—crown-5(L_c),having the compositions of M(NO_2)_2·L·nH_2O(M=Mn,Co, Zn,L=L_A,n=2;M=Cu,L=L_A,n=1.5; M=Cd, L=L_B,n=0; M=Cu,L=Lc,n=2) and AgNO_·L·nCH_3CN(L=LA,n=0; L=L_B,n=1; L=Lc,n=1/2) have been synthesized in nonaqueous solvent. All the isolated complexes have been characterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetric analysis, X—ray powder diffraction analysis, molar conductance and measuremends of solubility in some general solvents.     

Synthesis and Crystal Structure of [Pd(NH_3)_4]Cl_2·2[Pd(NH_3)_3Cl]Cl

PreparahonofsomecomplexcomPOundsof[Pd(NH3)41X2tw,tvhereX=Cl-,Br,I-,X2=Co,:-,RdChl'-,etc.,wasdescribedasearlyl942l'].SynthesisandcryStalstIUCtUreOfthesaltSt'ithamons,Cr2o7",Cro.:',MoO"',andC,o'=',ttcrestillreportedmorcrecenh/'-'j.IPd(NH)4lX2,tvhereX=Cl',BrandNOz,isanotherkindofamndnepalladiumcomplexcompounds.IntheSyStemofIPd(NH).1"-Cl'-H2o,diamlltinedichloridepalladium(II)wasObtalnedbythereachonOfIPd(NH)4lHcomplexionwtthanutebydrogenchloride,andtetrachloridepalladiumaDbythe…     

Syntheses,Structures, and Properties of Three Coordination Polymers: [Cd_2(bpp)_(1.5)(Hbpp)(phen)_2]_n, [Mn_3(Htptc)_2(phen)_2(H_2O)_2]_n,and {[Cu(btc)_(0.5)(1,4-bib)]·2H_2O}_n

Hydrothermal reactions of three aromatic polycarboxylic acids and the transitional metal cations in the presence of phen and 1,4-bib afford three new coordination polymers: [Cd2(bpp)1.5(Hbpp)(phen)2]n(1), [Mn3(Htptc)2(phen)2(H2O)2]n(2), and {[Cu(btc)0.5(1,4- bib)]·2H2O}n(3)(H2bpp = 2,6-bis(4'-carboxyphenyl)-4-phenylpyridine, H4tptc = terphenyl-2,5,2',5'-tetracarboxylic acid, H4btc = biphenyl-2,2',4,4'-tetracarboxylic acid, phen = 1,10-phenanthroline, and 1,4-bib = 1,4-bis(1H-imidazol-1-yl)benzene). Their structures have been determined by singlecrystal X-ray diffraction analyses, elemental analyses, IR spectra, and powder X-ray diffraction(PXRD) analyses. In compound 1, the CdII cations are linked by bpp2- to form one ladder structure, based on which a 3D network is constructed with the help of non-covalent interactions. The topology of 2 is a 3D(3,4,5)-connected framework with the Point Schl?fli symbol of(42.6)32(4.62.8)(45.64.8)2. Compound 3 shows an unprecedented 3D(4,4)-connected framework with the Point Schl?fli symbol of(64.82)2(65.8). Moreover, the luminescent property of 1 has been investigated.     

DNA Cleavage by Copper (Ⅱ) Complexes Without added Coreactants

Thedevelopmentofreagentswhichhydrolyticallycleave11ucleicacids"lidermildconditionsiscurrentlyattractinggreatinterestillthetieldofartiticialnucleases'-'.Whilemall}lreagentshavebeedsuccessfullyapplied.toDNAhydrolysis;.illershavebeenit-c'l'ersuccesseswithDNA'duetoitsrelativel}'highh}idrolyticstabilit}"(thepseudo-firsl-orderrateconstantt'Orthenollenzymatichydrolysisofphospllodiestersisextropolatedtobe2x10-"'h-=at24tandPH7.4').Theexceptionalstabilit}fofphosphodiestershasbeensuggestedasonereason…     

MOLECULAR AND CRYSTAL STRUCTURE OF (μ-4,4'-DIPYRIDYL)-BIS [DIAQUA-IMINODIACETATO-COBALT(Ⅱ)] TETRAHYDRATE {[CoNH(CH_2COO)_2(H_2O)_2]_2C_10H_8N_2}·4H_2O

<正> Mr=679.8,monoclinic, C2/m,a = 21.146(3), b = 12.613(1), c = 5.202(3)A,β= 93.26(2) ,V= 1385.1A3,Z = 2,Dx=1.63,Dm=1.64 g.cm-3 λ(MoKα)=0.71073A,μ=13.3cm-1,final R=0.036 for 1427 observed reflections. Bach cobalt atom in the title complex is in six-coordination environment with one bridging dipy ligand, two terminal H2O ligands and one tridentate ininodiacetic acid ligand. The "facial configuration" of the coaplex is compared with "the meridional one" found in corresponding Cu(II) complex.The bridge ligand dipy is tilted out of the coordination plane (N(1)-N(2)-O(1)-O(2) or N(1)-N(2)-0(1')-0(2')) by 47°,which may provide a spin-spin exchange pathway. Another possible magnetic exchange pathway is in the hydrogen-bonding linkage.     

Crystal Structure of Binuclear Bridging Complex[(dppf)_2Pd_2 (Ⅱ) (μ-Cl)_2] [PF_6]_2

1INTRODUCTIoNFerrocenecontainingtransitionmeta1complexeshasarousedtheinterestofchemistsbecauseofitsnovelstructureandproperties"',Huangetal[2'3isynthesizedsomechainandbridgeformcomplexesandstudiedtheirIRandCV.Linetal[4isyn-thesizedthecrystalof[(dppf)PdCl,jO.5[(CH3),COj(dppf=1,11-(diphenylphosphine)-ferrocene)anddeterminedthestructurebyX-raydiffraction.Inthisarticlewereportthesynthesisandcrystalstructureof[(dppf),Pd,(ll)(p-Cl),j[PF,j2.2EXPERIMENTAL2.1PreparationAsolutionofO.86mm…     

A One-dimensional Manganese(Ⅱ) Coordination Polymer with 4'-Hydroxybiphenyl-4-carboxylate as the Single Ligand:Synthesis,Crystal Structure and Luminescence

A new 1D coordination polymer,{[Mn2(4',4-hbc)4(4',4-Hhbc)2(H2O)]·H2O}n(4',4-Hhbc=4'-hydroxyl-biphenyl-4-carboxylic acid),has been hydrothermally synthesized and struc-turally characterized by elemental analysis,IR spectroscopy and single-crystal X-ray diffraction.The crystal belongs to the monoclinic system,space group C2/c with a=52.421(10),b=7.5388(15),c=16.478(3),β=106.12(3)°,V=6256(2)3,Z=4,C78H62Mn2O21,Mr=1445.16,Dc=1.534g/cm3,μ(MoKα)=0.490mm-1,F(000)=2992,R=0.0764 and wR=0.2006 for 2984 observed reflections with I2σ(I).X-ray diffraction analyses reveal that the title compound is a one-dimensional infinite chain,in which the MnⅡ atom adopts a distorted octahedral geometry coordinated by four 4',4-hbc ligands,one 4',4-Hhbc ligand and one water molecule.Furthermore,the luminescent property of title compound was investigated.     

Kinetics of Protonolysis of o-Substituted Phenylmercuric Chlorides by HCl(NaI) in Ethanol

Yadavetalhaveexaminedthereactionsbetweeniodineando-XC6H4HgCl(X=H,0H,CH3,N0z)inethanol,foundthatthetotalorderofthereacti0nwastwo,andthattheorderoftherateconstantsofthesedifferentderivativesofphenylmercuricchlorideis0H>H>CH3>NO2.Theyprop0sedthattheproximityofCH3grouptoHgCIgroup(orthoposition)isresponsibleforitsreverseeffect1.ButinourearlierresearhesonprotonolysisofarylmercuricchloridesbyHCl(NaI)inaqueousdio....2',n0obvioussterichindranceofo-substituentswasobserved,instead,abnormalelec…     

Ab Initio Theoretical Prediction on Structures of Boron Cationic Cluster B_(17)~+

BoronclustercompoundsrepresentdistinctivecovalentspecieswithauniquemoleculararchitectUre,nonconventionalclusterbonding,unusualchendstry.BoronistheelementsecondtocarboninitScapacitytobonditSelfandlargeclustersofthree-ddriensionallyconnectedboronatomsarewelldocumentedinvariousboronallotropes,boronhydridesandmetalborides,etc.'.However,littleisknownaboutbareboronclusters.Recently,aseriesofsignificantexPeriInentSonisolatedB-(n=2-l7)"'andB.(n=2-52)'havestronglystAnulatedtheoreticalinvestigations…     

双核Cd(Ⅱ)配合物[Cd2(C22H14N4)2Cl2(N3)2]2·H2O的合成与晶体结构

A dinuclear Cd(Ⅱ) complex [Cdz (N3)2LzCl2]2·H2O (1) [L=4'-(4-eyanophenyl)-2,2':6',2"-terpyridine]was synthesized by reaction of ligand L with CdCl2 and NaN3 using solvothermal method and its structure was determined by X-ray crystal structure analysis. The structure indicates that the complex crystallizes in monoclinic, space group C2/c with a=1.644 5(16) nm, b=1.441 9(12) nm, c=1.9181(18) nm,β=100.349(11)°. V=4474(7) nm3, Z=2, Dc=1.570Mg·m-3,μ=1.120 mm-l, F(000)=2 100, and final R1=0.039 3, wR2=0.0811. The result shows a Cd(Ⅱ) ion was sixcoordinated by a tridentate 4'-(4-cyanophenyl)-2,2' :6',2"-terpyridine ligand and one bridging nitrogen atom of the azide group in the basal position and an chloride atom and the other bridging nitrogen atom of the azide group in the axialone, to form a distorted octahedral-pyramidal geometry. CCDC: 673291.     

Catalytic Asymmetric Cyclopropanation using a New Chiral β-Diketone Cu (Ⅱ) Complex as a Catalyst

ManytransitionmetalcomPlexescatalyzethedecomPositionofa-diazoesterbythemethylenetransferreactiontoolefins,givingthecorrespondingcyclopropaneadductsl'z.Thismethodhasbeenwidelyusedinthesynthesisofnaturalproducts.Sofar,variouskindsoftransitionmetalcomPlexeshavebeenusedintheasymmetriccyclopropanation"'.6-diketonecomplexessuchasCu(acac)2(acac=acetylacetone)areamongthemostpopuIarcatalystsforthecyclopropanationofalkeneswithdiazocomPounds,butthefirstchiralo-diketonecomplexwasreportedonlyinl9845.Wesy…     

Synthesis and Crystal Structure of Cobalt(Ⅲ) Tris(diethyldithiocarbamato) Complex

1INTR0DUCTI0NRecently,thedesignandsynthesisofdinuclearcomplexeshavebeenafascinat-ingareaofresearchowingt0theirimportanceinbasicandappliedchemistry"'.Par-ticularintersthasdevelopedindinuclearcomplexesasmodelsformeta1loproteins"'.Inanattempttosynthesizethetypeof[Ln(S,CN(C2H,)2)3j[Co(S2CN(C2H5)2)2jdinuc1earcomplex,thepurefinecrystalsofCo[S2CN(C2H5)2)2)3were0btained.2EXPERIMENTAL2'1Preparation0fC0[S,CN(C,H,),j,TotheclearsolutionoftheanhydrousSmCl3(0.5mmol)in5mLanhydrousethanolw…     

Cu(Ⅰ)配位聚合物[Cu_3(CN)_3(3-pytpy)]_n的合成、晶体结构及其荧光性质

在160℃下,以4'-(4-吡啶基)-3,2'∶6',3″-三联吡啶(3-pytpy)为配体,Cu(OAc)2·H2O为金属盐,通过水热法在乙腈/水的混合溶剂中合成了一个Cu(Ⅰ)配位聚合物[Cu3(CN)3(3-pytpy)]n(1)。通过元素分析、红外光谱、X-射线粉末衍射和热重分析对所合成的配合物进行了表征,并用X-射线单晶衍射分析确定了晶体结构。结果表明,其晶体属单斜晶系,空间群为P21/c,Mr=579.03,a=7.132(6),b=17.431(13),c=18.388(13),β=94.284(14)°,V=2280(3)3,F(000)=1152,Z=4,μ=2.799mm-1,Dc=1.687g/cm3,最终残差因子R1=0.0447,wR2=0.1238。Cu(Ⅰ)均为畸变三角形配位模式,配位原子分别为三联吡啶配体吡啶环上的N原子、CN-基N原子和另一个CN-基C原子。CN-基桥联Cu(Ⅰ)离子形成沿ac平面对角线方向延伸的一维内消旋螺旋链[Cu(Ⅰ)-CN]n,配体3-pytpy则进一步桥联这些一维链形成二维"波浪型"网络结构,2D层以ABAB方式堆积并通过吡啶环间的π…π堆积作用拓展为三维超分子结构。     

Synthesis and Crystal Structure of 1-(o-methylphenyl)-2-(p-methoxyphenyl)-1,3,2-diazaphospholidin-4-thione-2-sulfide

11NTRODUCTIoNThederivativesofdiazaphospholidinoneorthecorrespondingthionesareknowntopossessinterestingbiologicalproperties,suchasherbicidalactivity"'2i.Inrecentyears,itwasreportedthatthel,4,2-diazaphospholindine-5-thione-2havegoodselectiveherbicidalactivity"'41.Tolookformoreeffectiveherbicideswithlowtoxicity,aseriesofnovel1-(o-methylphenyl)-2-(p-methoxyphenyl)-phospholidin-4-thione-sulfideshavebeensynthesizedandtheirmolecularstructuresstudied.PreliminarybioassaysshowthatthesecomPoundshaveg…     

B_n(BO)_n~(2-)、CB_(n-1)(BO)_n~-和C_2B_(n-2)(BO)_n(n=5~12):类似于笼状B_nH_n~(2-)、CB_(n-1)H_n~-和C_2B_(n-2)H_n的硼氧团簇

笼状硼氢化合物BnHn2-、CBn-1Hn-和C2Bn-2Hn(n=5~12)含n个顶点和(n+1)对骨架电子,具有典型的三维芳香性、高的芳香化能和类似于苯的化学反应性.2005年以来,在研究B-O二元团簇的过程中,我们首次提出硼的硼羰基化合物(boron boronyls)和碳的硼羰基化合物(carbon boronyls)的概念,探讨了Bn(BO)m0/-1/-2(n=1~2,m=2~4)及Cn(BO)n(n=3~7)系列化合物的几何结构和电子性质.基于高分辨光电子能谱实验和密度泛函理论分析,确认线性B(BO)20/-1及三角形B(BO)30/-1新颖结构,首次发现线性D∞h B2(BO)22-离子含有B≡B三重键.理论和实验结合研究表明,BO与H具有等瓣相似性,BO自由基具有类似于CN的化学行为.在此基础上,本文用BO基团取代BnHn2-、CBn-1Hn-及C2Bn-2Hn(n=5~12)中的H原子,形成Bn(BO)n2-、CBn-1(BO)n-及C2Bn-2(BO)n(n=5~12)系列硼氧化物,对其几何和电子结构、稳定性和芳香性进行密度泛函B3LYP/6-311+G(3df)理论研究.图1给出n=1...     

Synthesis and catalytic activity of novel heteronuclear Ln(Ⅲ)-Cu(Ⅱ) complexes with noncyclic polyether-amino acid Schiff base

A series of novel heteronuclear Ln(Ⅲ)-Cu(Ⅱ) complexes with noncyclic polyether-amino acid Schiff base were synthesized. The general formula is [LnCu_2(H_2TALY)(NO_3)_5](NO_3)_2' nH_2O(Ln=La, Nd, Sm, Gd, n= 4; Ln=Yb, Y, n=3), where H_2TALY = tetraglycol aldehyde bis-lysine Schiff base. It is the first time to report the synthetic method for this new Cu(Ⅱ) complexes and Ln(Ⅲ)-Cu(Ⅱ) heteronuclear complexes. The complexes were characterized by elemental analysis, IR spectra, TG-DTA, magnetic susceptibility, and especially by a 500 MHz NMR spectrometer for 2D-COSY NMR. Coordination mechanism and structures of complexes have been suggested as well. Of particular interest is the potential that the novel complexes obtained may be used as a catalyst, which prompted us to investigate them. It shows 100% conversion with the viscosity-average molecular weight 120 000 for the polymerization of methyl methacrylate (MMA) without addition of any cocatalyst. Furthermore, the complexes with such aliphatic Schiff bas     

Hydrothermal Synthesis and Crystal Structure of a Novel Dinuclear Co(Ⅱ) Complex: [Co2(2,2(')-bpy)2((-L)2(L)2(μ-H2O)] (HL = 4-Chlorobenzoic Acid)

A new 4-chlorobenzoic acid bridge Co(Ⅱ) complex [Co2(2,2(')-bpy)2(μ-L)2(L)2(μ- H2O)] (HL = 4-chlorobenzoic acid) has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group C2/c with a = 22.537(5), b = 16.212(3),c = 15.306(3)(A), β= 124.37(3)°, V = 4616.1(16) (A)3, Mr = 1070.45, Dc = 1.540 g/cm3, Z = 4, μ = 1.012 mm-1, F(000) = 2176, the final R = 0.0338 and Wr = 0.0810. The title complex is composed of dinuclear [Co2(2,2(')-bpy)2(μ-L)2(L)2(μ-H2O)] molecules. Each Co(Ⅱ) atom is coordinated by two nitrogen atoms from one 2,2'-bipyridine ligand, three oxygen atoms from three 4-chlorobenzoic ions and another oxygen atom from one water molecule. The two Co(Ⅱ) atoms are connected by two 4-chlorobenzoic ions and one bridged water molecule. The dinuclear molecules are interlinked by hydrogen bond and π-π stacking interactions into a three-dimensional supramolecular network.     

(HAINH)_n(n=1～6)簇的结构、红外光谱和热力学性质的研究

用自洽场理论(HF)和密度泛函理论(DET)的B3LYP方法,在6-31G~μ水平上研究了HAINH的低聚物(HAINH)_n(n=1～6)簇的几何构型、电子结构、红外光谱和化学热力学性质,并比较了(HAINH)_n和(CIAINH)_n两种低聚物对应结构中化学键强弱,分析了引起(AIN)_n骨架结构发生变化的原因.结果表明,(HAINH)_n簇的基态结构为C_8(n=1),D_(2h)(n=2),D_(3h)(n=3),T_d(n=4),C_s(n=5)和D_(3d)(n=6)对称点群.HAINH基态结构中,AI-N键是三重键.在D_(2h)(n=2)和D_(3h)(n=3)结构中,所有AI-N键均为二重键.在Td(n=4)和D_(3d)(n=6)中,AI-N键为正常单键,而在C_s(n=5)结构中含有三种AI-N键:单键、双键和混合键.振动频率计算表明,结构a～f均为基态稳定结构.热力学计算给出的稳定性顺序为:f>d>e>c>b>a.     

五配位Cu(Ⅰ)配合物[Cu(4'-Phtpy)(PPh3)2](BF4)的合成、结构及光谱性质研究

由[Cu(MeCN)2(PPh3)2](BF4)和4'-苯基-2,2':6',2"-三联吡啶(4'-Phtpy)在室温下反应,合成了一个新颖的具有光致发光性能的五配位配合物[Cu(4'-Phtpy)(PPh3)2](BF4).对配合物进行了X射线衍射结构表征,并进行了红外光谱、紫外可见光谱、荧光光谱等光谱学分析.晶体属单斜晶系,空间群Pn,晶胞参数:α=1.0807(6)nm,b=1.0943(6)nm,c=2.1610(12)nm,α=90°,β=102.785(10)°,γ=90°,V=2.492(2)nm3,Z=2,Dc=1.354g@cm-3.配合物中,Cu(Ⅰ)与4'-Phtpy的3个N,2个PPh3的P配位呈变形三角双锥型结构,其轴向由Cu键合联吡啶的末端2个N所组成,赤道平面由联吡啶的中心N原子和2个PPh3的P原子所组成.