簇合物〔WOS_3 Ag_3 Br(PPh_3)_3〕·(OPPh_3)的合成和晶体结构

报道了〔WOS3Ag3Br(PPh3) 3〕·(OPPh3)簇合物 (C72 H6 0 Ag3BrO2 S3P4W ,Mr=176 4.6 1)单晶的合成和结构。该晶体属于三方晶系 ,空间群为R3 ,晶胞参数 :a =16 .14 0 (3) ,c =2 3 .0 0 3(4) ,V =5 189.4(15 ) 3,μ(MoKα) =3 .2 98mm- 1 ,Z =3 ,F(0 0 0 ) =2 5 98,Dc=1.6 94g/cm3。独立衍射点 2 181,可观察衍射点 195 2 (I≥ 2σ(I) ) ,R =0 .0 496 ,wR =0 .12 48。该晶体由簇合物分子〔WOS3Ag3Br(PPh3) 3〕和以P为中心的扭曲四面体结构的中性分子OPPh3 构成 ,其中的簇合物分子的骨架为由1个W原子、3个S原子、3个Ag原子和 1个Br原子构成的立方烷状。W、O(1)和Br原子位于C3轴上。     

Crystal Structure of 〔PdCl_4〕·〔C_4H_(10)NO〕_2 Compound

INTRODUCTIONPalladiumcomplexesplayanimportantroleinmanycatalyticreactions,especial-lyincarbonylationofolefins.InordertostudytherelationshipbetweenthestructureandproPertyofpalladiumcomplexcatalyst,thetitlecomplexwassynthesizedanditsstructurewascharacterizedbyX-raydiffractionmethod.2EXPERmENT2.1SynthesisAmixtureofmorpholine(o-lmol)andCuCl(O.2mol)inmethanol(8OmL)wasrefluxedfor6h.AftercoolingthesolutionwasfilteredrePeat-edlyunti1theclearfiltratewasobtained.BrownCuCl.C'H,NOcrystalswer…     

Multinuclear Nuclear Magnetic Resonance Studies of 〔VS_4 (CuPPh_3)_5 (CuCl) Br_2〕

11NTRoDUCTIONThecomplexchemistryofthetetrathiometallatestMS,j"-(M=Mo,W,n==2lM=V,n=3)hasbeenextensivelyinvestigatedbecauseofitspotentialutilityinimi-tationofbiologicalsystems"'.Especially,vanadium-containingheterometallicsulfurcomplexesareofinterestasmodelsoftheactivesitesinmetalloenzymestobiomimeticchemistst2'33.Studiesonthiometalateandrelatedmultimetalcomplexeshavebeenmain1yaboutsynthesesandcrystalstructures,butNMRinvestigationswereraret43.SinceNMRspectroscopyrespondstothemagneticpro…     

〔NEt_4〕〔CoCl_3(PPh_3)〕的合成和晶体结构

标题化合物是反应体系 (NH4) 3VS4/CoCl2 (PPh3) 2 /NEt4Cl在CH2 Cl2 中反应而得到的 ,单晶X射线结构分析表明 :其晶体属于立方晶系 ,化学式为C2 6 H35 NCl3CoP ,空间群为Pa3 ,Mr=5 5 7.84,a =17.80 7(5 ) ,V =5 6 46 .4 3,Z =8,Dc=1.31g/cm3,F(0 0 0 ) =2 32 8,μ(MoKα) =9.6cm- 1 ,R =0 .0 6 2 ,Rw =0 .0 6 7。标题化合物分子结构具有结晶学三次轴对称性 ,Co(II)原子为四面体配位 ,键角Cl-Co -Cl(113 .4(2 )°)大于键角Cl-Co -P(10 5 .2 (2 )°)。同时也讨论了标题化合物的电子光谱和变温磁化率     

Structure of 〔Pyridine(tris(2-aminothylamine〕copper(Ⅱ) Diperchlorate 〔Cu(C_6H_(18)N_4)(C_5H_5N)〕(ClO_4)_2

1INTRoDUCTIONInvestigationsofthecoordinationchemistryofcopper(I)continuebeingstimu-latedbyinterestindevelopingmodelsforcopperproteinandinunderstandingthefac-torswhichgivetotheseeminglyinfiniteverityofdistortionformregularstereo-chemistryobservedinCu(U)comp1exest"23.Duetotheuniquecoordinationpolyhe-dron,importanceinbiochemistryandtheireaseofpreparation,tripodalcopper(I)complexeshaveattractedmucha!tentioninadditiontotheirspecialchemicalphysicsandstructureproperties.Wereportherethesynthesis…     

六棱柱型金属团簇化合物W2Ag4S8(dppy)4的纳秒光限幅特性

新合成了一种金属团簇化合物W2Ag4S8(dppy)4,(分子式为C68H56Ag4N4P4S8W2)并用X-射线单晶衍射结构分析方法测定了其晶体结构.单晶X-射线衍射数据表明这种金属团簇化合物具有六棱柱型.在纳秒激光脉冲作用下研究了W2Ag4S8(dppy)4的二甲基甲酰胺(DMF)溶液的光限幅特性.实验结果表明W2Ag4S8(dppy)4的DMF溶液在放置一段时间后光限幅特性明显优于新配制的DMF溶液,其光限幅特性明显强于C60甲苯溶液,表现出其具有较强的光限幅特性.为了研究W2Ag4S8(dppy)4的光限幅机制及光限幅特性在放置一段时间后发生变化的原因,又做了非线性散射和泵浦探测实验,并对其光限幅机制和光限幅特性在放置一段时间后发生变化的原因进行了分析.     

Synthesis and Crystal Structure of 〔Na(N-(p-chlorophenyl)aza-15-crown-5)-(Et_2O)〕_2 (Na_2W_(0.5)Mo_(7.5)O_(26))

1mThODUCnONThestudyofsupermolecularcomplexesofcrownetherringhasthrivedforyearsrecentlybecauseoftheirprobabilityprospectinmaterialscienceandlifescience,andtheirinterestingstereochemistrywhentheradiusofcavityofringischanged"'.Inthecourseofourinvestigationontherelationshipbetweenthesizeofthecrownetherringandthepolymerizationofpolyoxometalate,anovel'crystalofsupermolecularcomplexof[Na(N--(p--chlorophenyl)aza--15--crown--5)(Et,O)j2(Na,W,.5Mo,.5O,,)wasobtained.2EXPERIMENTALToasolutionofequ…     

Solid State Synthesis and Structural Characterization of the Compound H_2 [(n-Bu)_4N]_3 [As (SiW_(11)O_(39))]

1INTRODUCTIONThereactionsoftheundecatungstosilicate{SiW,,O,,j'-withmetalornon-metalionshavebeenextensivelyinvestigated"'-Sofar,mostofthesereactionsreportedintheliteraturehavebeenpreparedeither1nsolutionorunderthehydrothermaIcondi-tion.Recently,wehavepreparedMo(W)-Cu(Ag)-Sclustersbysolidstatereac-tionsatlowheatingtemperatures""'.Asanextensionofthisresearch,wereportherewiththesynthesisandcrystalstructureofH,[(n-llu),Nj,[As(SiW,,O,,)j.2EXPERIMENTALThetitlecompoundwasobtainedbyheat…     

Synthesis and Structure of 〔Cu(Hcdta)〕(H_2O)

1mTRODUCTION.Theimportantprogressinmagnetostructuralchemistryinthepastfewyearsisthesystematicdevel0pmentofstructurallyorderedbimetalliccompound"'.Thefami-liesofcrystallineandam0rphouscomplexes[MM'(cdta)j.xH,O(M,M'maybethefirsttransitionmetalorthesecondmaingroupelements)haveprovidedniceex-amplesofstructuralversatilityinmagneticstudiest2-6i,wherequiteafewstructuresmentionedabove,includingbimetallicandhomometalliccompoundscomprisingcop-per0rothermetalatoms,havebeeninvestigated"-".Ontheother…     

Synthesis and Structure of the Copper(Ⅰ) Complex 〔Cu(PPh_3)_2(BH_4)〕

1　INTRODUCTIONCopper( ) displayswide diversity in itsstructuralchemistry,the copper coor dination number ranging from two to four.Procedures to synthesize copper( )complexes itself are of great interest because of the diversity of products resultingfrom almost the same methodology.Ithas long been accepted that because copper( ) complexesare diamagnetic,and hence,provideno opticalabsorption bands( nod d transition is encountered) for a copper( ) ion with a d10 configuration and noelect…     

Crystal Structure of 〔(Ph_3P)_2N〕〔FeCo_3(CO)_(12)〕

lINTRODUCTIONThefirstheteronucleartransitionmetalclusterHFeCo,(Co),,wassynthesizedbyChinit13in196Obyusingthepyrolysisofmeta1carbonyldimers.Analysisofcar-bonylIRspectraandX-raypowderpatternsindicatedthatthiscompoundisisostruc-tural.withCo'(CO),,andthushasC,.symmetry(".MaysE'-'ihascarriedoutIRspectraandmassspectraonthiscompoundandkineticisotopestudiesontheprotona-tionoftheanion[FeCo,(CO),,j-,andproposedonthebasisofthisevidencethatthehydrogenatommightbelocatedinthecenterofthecluster.…     

四核银原子簇化合物Ag_4(α-C_(10)H_7CS_2)_4(Py)_4·2Py的晶体结构

四核银原子簇化合物Ag_4(α-C_(10)H_7CS_2)_4(Py)_4·2Py由α-萘荒酸与硝酸银在有机溶剂中反应,经吡啶重结晶获得单晶。由于反应中采用不同的银盐与α-萘荒酸的投料比(1:2与1:4),得到了两种颜色的晶体(甲和乙)。用X射线单晶衍射法测定了它们的晶体结构。晶体甲的空间群为C_(2h)~5—P2_1/a。晶胞参数:a=2.2822(4)(?),b=12.803(4)(?),c=24.444(7)(?),β=103.90(2)°,V=6933.14(?)~3,Z=4。晶体乙的空间群为c_(2h)~6—c2/c。晶胞参数:a=29.150(2)(?),b=12.789(3)(?),c=24.413(2)(?),β=130.56(4)°,V=6914.38(?)~3,Z=4。Ag_4(α-C_(10)H_7CS_2)_4(Py)_4在两种晶体中的空间构型基本相同,差别只在于分子的对称性上。晶体乙中,分子处在二重轴上,分子的对称性较高。本文只报道晶体乙的结构测定和结构参数.3338个反射参与修正,最终的偏差因子R=0.093。分子中Ag_4呈压扁的四面体构型。六个Ag—Ag距离可分成两类,硫桥相连的Ag—Ag平均键长为2.924(?)(2.875—2.972(?)),表明有相当程度的金属键相互作用。不与硫桥相连的Ag—Ag距离为3.563(?)。     

原子簇配合物〔(C_4H_9)_4N〕_2〔Mo_2S_6O_2〕的合成、结构和性质研究

用(NH_4)_2MoS_4、FeCl_3和(C_4H_9)_4NBr在CH_3OH-CH_3ONa溶液中反应,得到了原子簇配合物[(C_4H_9)_4N]_2[Mo_2S_6O_2]晶体,用X-射线单晶衍射方法测定了簇合物的晶体结构,晶体属空间群D_(2h)~(15)-P_(c a h),晶胞参数为a=15.876(3),6=17.786(6),c=31.90(1),V=9008.7~3,经块矩阵最小二乘法修正,最终得偏离因子R=0.0659,同时对簇合物的红外光谱、拉曼光谱、紫外可见光谱以及电化学性质也进行了研究。     

Molecular and Crystal Structure of 4-〔2-(4-Dimethy aminophenyl)ethenyl〕-1-methypyridinium tetraphenylborate

1　INTRODUCTIONAccordingtotheorganic“saltmethodology”principle〔1〕,whichsuggeststhatCoulombicinteractionsinorganicsaltscouldoverridedipolarinteractionswhichpro-videastrongdrivingforceforcentrosymmetriccrystallizationindipolarmolecularcrystals,asystematicsearchforSHG(SecondHarmonicGeneration)organiccrys-talswasconducted.AsearchontheCambridgeStructuralDatabase〔2〕(Version5.18)wasdonefororganicsaltshavinganionBPh4-(47cmpoundsintotal)orBF4-(147compoundsintotal)andcationcontainingatle…     

Li_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3,Na_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3的离子交换研究

研究了在不同温度下的NaNO3和AgNO3水溶液中Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3离子交换行为.实验表明Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3均显示出了高选择性与Na+和Ag+进行离子交换的特征,且对Ag+的选择性高于Na+.升高温度可显著提高Ag/Li和Ag/Na的交换反应速度.     

CRYSTAL STRUCTURES OF [Bu4N]2[M2Ag3（ μ3—S）2（μ—S）4S2Et2dtc]（M=W,Mo）

<正> The title compounds were prepared from the reation of (NH4)2MS4 (M=W,Mo),AgNO3,NadtcEt2 and Et4NBr in CH3CN-H2O solution. The isomorphous compounds [Bu4N]2[W2Ag3S8Et2du] ( I ) and [Bu4N]2[Mo2Ag3S8Et2dtc] (Ⅱ) crystallize in triclinic space qroup Pi with the following crystal parameters:α=13. 043(4),b = 21. 640(6),c=10. 757(6)A ,α=95. 09(5),β = 91. 90(4),γ = 98. 57(3)°,Z = 2,V = 2987A3,Dc=1. 76g/cm3 for I 5;a= 12. 989(2) ,b=21. 574 (9) ,c= 10. 7/1(1) A .α= 95. 06(7), β=91. 61(4), γ=98. 52(2)°, Z = 2,V = 2961 A3.Dc= 1. 58g/cm3 for Ⅱ . The final R and Rw values are 0. 061 and 0. 072 for Ⅰ ,and 0. 062 and 0. 076 for Ⅱ The M2Ag3 (M = W, Mo) unit in anion M2Ag3S8Et2dtc forms a five-membered ring.     

CRYSTAL STRUCTURE OF W_4(μ_(3-)S)_4[S_2P(OEt)_2]_6

<正> W4S4 [S2P (OEt)2]6, Mr= 1974. 94, triclinic, P1, a = 14. 063 (5) , b = 16. 289(4), c= 13. 377(3) A ,α=92. 06 (2), β=95. 24(3), γ= 73. 06(2)°, V= 2919(3)A3,Z=2,DC=2. 18g/cm3, Moka radiation,λ =0. 71069A ,μ = 90. 64cm-1, F(000) = 1764,R=0. 053 and Rw = 0. 069 for 5422 reflections with I≥3σ(I).The title compound is comprised of a cubane-like cluster core [W4S4] in which every W atom is coordinated by six S atoms to form a distorted octahedron.     

Synthesis and Crystal Structure of a Novel Polymeric Complex [WS4Cu4（PY）4（μ-CN）2]∞

1 INTRODUCTION The synthesis of Mo(W)/Cu(Ag,Tl)/S polymeric complexes from the reactions of [MS4]2- (M = Mo, W) with Cu , Ag or Tl remains attractive due to their rich coordination chemistry[1～10] and NLO ma- terials[7, 10]. For example, the reacti…     

异金属螺旋链化合物{[W_6Ag_6S_(24)][La(DMSO)_8]_2}_n的合成及结构表征

合成了异金属含硫化合物{[W6Ag6S24][La(Me2SO)8]2}n,并用X射线单晶衍射法测定了其结构.结果表明,该化合物属三斜晶系,P-墿空间群;晶胞参数为:a=1.577 5(3),b=1.818 7(4),c=1.952 3(4)nm,α=92.210(2)°,β=106.567(3)°,γ=92.494(2)°,Z=2,Dc=2.510 g/cm3,μ=9.081 mm-1,F(000)=3 792,R1=0.040 9,wR2=0.086 9.化合物中的阴离子[(W6Ag6S24)6-]n具有异金属螺旋链结构,所有W原子和Ag原子均与S原子形成四面体配位构型.     

A New Ionic Trimolybdenum Cluster Compound:〔Mo_3S_7(S_2P(iprO)_2)_3〕〔S_2P(iprO)_2〕

1INTRODUCTIoNInthepastdecades,thechemistryofMo-Sclusterscontaininga[Mo,(p,-S)(p-S,),j corehasbeenstudiedtextensively,andmanysuchkindofcompoundshavebeensynthesized.(1'2'3'4iHowever,fewcompoundscontainingadiscreteclus-tercationhavebeenreported.[5iInthispaper,wereportthesynthesisandstructureofthetitlecompound.Thisisanewexampleoftrimolybdenumclustercontainingadiscreteclustercation.2EXPERIMENTALAllmanipulationwerecarriedoutinair.2.1Synthesis0f[M0,S,(S,P(iprO),),jtS,P(iprO),jAmixture…