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IntroductionTheexpensionofthecoordinationchemistryofpolyoxomolybdatesisattributedtothesolubilityofthepolyoxometallicanionsinorganicsolventsandcoordi nationabilityofthemascharacteristicmetalligandsinorgano metallicreactions ,forexample ,thestudyofcatalys… 相似文献
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1 INTRODUCTIONSincethiolateligandwasintroducedintomolybdenumcarbonylcompoundin1 984 [1],theinvestigationonlow valenceMo -SRcompoundshasreceivedattentionforthiskindoflow valencecompoundspossesscertainadvantageoncompoundsyn thesis,moleculestructureandphysicala… 相似文献
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Itiswellknownthatinnaturetheactivationandreductionofdinitrogeninairtoammoniaarecatalyzedbynitrogenaseatambienttemperatureandpressure.ThemaincomponentsoftheactiveclusterofMoFeproteininnitrogenaseareMcluster(MoFe7S9cluster)andPcluster(Fe8S8cluster)[1].Inthel… 相似文献
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ZHENG Yue qing * 《高等学校化学研究》1999,(3)
IntroductionPreviously,wereportedthecrystalstructureofK2[Ni(CO3)2(H2O)4][1],whichcrystallizedinthebaylissitetypestructureandwasfoundtobeisostructuralwithK2[Co(CO3)2(H2O)4][2]andK2Mg(CO3)2·4H2O[3].Inordertosystematicallyinvestigatetheoccurrenceoftheco… 相似文献
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Recently ,therehasbeenagrowinginterestincoor dinationpolymers1withaone (1 D) ,two (2 D)orthree dimensional (3 D)structure .Theuniquephysico chemicalpropertiesofthesepolymers ,highthermalsta bility,2 gasadsorptionanddesorption ,3 smallmoleculesocclusion ,4 ionexchange5… 相似文献
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Thetrimolybdenumclusterswithgeneralformula[Mo3(μ3S)(μS)3(μdtp)(dtp)3L](dtp=(S2P(OC2H5)2)-,L=H2O,py,SC(NH2)2etc.)[1](referredtoasM1type[2]),and[Mo3(μ3S)(μS2)3(dtp)3]X(X=Cl,I)[3](referredtoasM2type),aretwomaintypesoftrimolybdenumclusterseverinvestigatedbyourresearchgroup.Aswehavealready… 相似文献
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IntroductionInthelasttwodecadesintensivestudieshavebeencarriedoutonthemolybdenum (tungsten)chalcogenideclusters ,resultinginthediscoveryofseriesofmonomer ic ,polynuclearMo(W ) andMo(W ) heterometallicco mplexes .Triangular ,cubane ,octahedralaswellashex nuclear… 相似文献
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IntroductionThesupramolecularcomplexeformedbytheweakinteractions (electrostaticinteraction ,hydrogenbonds ,vanderWaalsforce ,short rangeexclusionforce ,etc .)ofmorethantwosortsofspeciesisanorganizingentitythatusuallypossessesspecialstructureandfunction .1Sup… 相似文献
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CompoundsformedfromCu ,AgandAuwithdithio lateligands ,suchasthedialkyldithiocarbamate (DTC) ,mercaptothiazoline (HMT)anddialkyldithiophosphates(DDP) ,haveplayedanimportantroleintechnology .1Cu(I) Sclustersalsohavebeenimplicatedinbiologyasan ti oxidants .2Thecuban… 相似文献
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The compounds [(n‐Bu)4N]3[MoS4Ag3Cl4] ( 1 ) and [Et4N]3[WOS3Cu3I4] ( 2 ) were synthesized and characterized. Compound 1 crystallizes in the rhombohedral system, space group R3c with a = 17.194(1), b = 17.194(1), c = 39.194(3)Å, Z = 6, V = 10034.7(11)Å3. Compound 2 crystallizes in the rhombohedral system, space group R3c with a = 14.461(2), b = 14.461(2), c = 34.952(2)Å, Z = 6, V = 6329.9(13)Å3. The X‐ray crystallographic structure determinations show that these two cluster compounds consist of a slightly distorted cubic core. Nonlinear optical (NLO) properties of these two clusters were investigated by using Z‐scan techniques with an 8 ns pulsed laser at 532 nm; both clusters exhibit strong nonlinear optical absorption effect (effective α2 = 1.18 × 10—10 m · W—1 for 1 and 1.0 × 10—10 m · W—1 for 2 ). 相似文献
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The hydrothermal reaction of CuBr2 and CuBr with phen·H2O (phen= 1,10-phenanthroline) in a molar ratio of 1:1:1.5 gave birth to the first copper-halo cationic cluster [Cu2^Ⅱ Cu2^Br4 (phen)4 ] ^2+(1) with tetranuclear anionic cluster [Cu4Br6]^2-. Changing the precursors or their molar ratios, two mononuclear complexes [Cu(phen)2Br]Br·H2O (2) and [Ni(phen)3][CuCl2]2 (3) as well as two unusual copper-halo chains found in polymers [Cu2Br2(phen)]∞ (4) and [Cu^ⅡCu3^ⅠBr2Ⅰ3 (phen)2 ]∞ (5) were obtained. The (Cu2Br2)∞ chain of 4 looks like a linearar ray of hexagons based on fused Cu3Br3 units, and the linear (Cu3Ⅰ3Br^-)∞ chain of 5 is an alternate combination of the rhombic Cu2I2 cores and the Cu4I4Br2^2- units. In addition, the hydrothermal reaction of CuBr2 with NA(NA=nicotinic acid) or INA (INA =isonicotinic acid) resulted in the syntheses of two compounds [CuBr(NA)] (6) and [CuBr(INA)]∞(7) containing staircase chain. Among them the third-order non-linear optical properties of 2, 5, 6 and 7 were investigated and all exhibit the reverse saturable absorption (α2〉0) and self-defocusing performance (n2〈0). 相似文献
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IntroductionTetrathiometallateanions [MS4 ]2 - (M =Mo ,W )andtheirclusterswithvarioustransitionmetalsarewell knownfortheirrichcoordinationchemistry ,1 7andtheirrelationtoindustrialcatalysisprocess ,8biologicalsystems ,9andNLOmaterials .10 12 However,thechemistryoftheorganometallictrisulfidecomplexes [PPh4 ][(η5 C5Me5) MS3](M =Mo ,13W14 )andtheirrelatedmixed metalclus tershavebeenlessinvestigated .15,16 Inordertoextendourknowledgeaboutthechemistryof [PPh4 ][(η5 C5Me5) MS3]andconti… 相似文献
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Michael Ruck 《无机化学与普通化学杂志》1997,623(10):1591-1598
Bi24Ru3Br20: A Pseudo-Tetragonal Structure with [RuBi6Br12] Clusters and [Ru2Bi17Br4] Groups The melting reaction of Ru with Bi and BiBr yields black, lustrous, air insensitive crystals of the subbromide Bi24Ru3Br20. The orthorhombic crystal structure (space group Pc21n, a = b = 1377.8(1) pm, c = 3222.3(4) pm, V = 6117.0 · 106 pm3) deceives pseudo-symmetry with respect to the tetragonal space group P4/ncc leading to multiply twinned crystals. The structure can formally be subdivided in [RuBi6Br12] clusters, [Ru2Bi17Br4] stacks, and [BiBr4] groups. 相似文献
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Alkoxo Compounds of Iron(III): Syntheses and Characterization of [Fe2(OtBu)6], [Fe2Cl2(OtBu)4], [Fe2Cl4(OtBu)2] and [N(nBu)4]2[Fe6OCl6(OMe)12] The reaction of iron(III)chloride in diethylether with sodium tert‐butylat yielded the homoleptic dimeric tert‐‐butoxide Fe2(OtBu)6 ( 1 ). The chloro‐derivatives [Fe2Cl2(OtBu)4] ( 2 ), and [Fe2Cl4(OtBu)2] ( 3 ) could be synthesized by ligand exchange between 1 and iron(III)chloride. Each of the molecules 1 , 2 , and 3 consists of two edge‐sharing tetrahedrons, with two tert‐butoxo‐groups as μ2‐bridging ligands. For the synthesis of the alkoxides 1 , 2 , and 3 diethylether plays an important role. In the first step the dietherate of iron(III)chloride FeCl3(OEt2)2 ( 4 ) is formed. The reaction of iron(III)chloride with tetrabutylammonium methoxide in methanol results in the formation of a tetrabutylammonium methoxo‐chloro‐oxo‐hexairon cluster [N(nBu)4]2[Fe6OCl6(OMe)12] ( 5 ). Crystal structure data: 1 , triclinic, P1¯, a = 9.882(2) Å, b = 10.523(2) Å, c = 15.972(3) Å, α = 73.986(4)°, β = 88.713(4)°, γ = 87.145(4)°, V = 1594.4(5) Å3, Z = 2, dc = 1.146 gcm—1, R1 = 0.044; 2 , monoclinic, P21/n, a = 11.134(2) Å, b = 10.141(2) Å, c = 12.152(2) Å und β = 114.157(3)°, V = 1251.8(4) Å3, Z = 2, dc = 1.377 gcm—1, R1 = 0.0581; 3 , monoclinic, P21/n, a = 6.527(2) Å, b = 11.744(2) Å, c = 10.623(2), β = 96.644(3)°, V = 808.8(2) Å3, Z = 2, dc = 1.641 gcm—1, R1 = 0.0174; 4 , orthorhombic, Iba2, a = 23.266(5) Å, b = 9.541(2) Å, c = 12.867(3) Å, V = 2856(2) Å3, Z = 8, dc = 1.444 gcm—1, R1 = 0.0208; 5 , trigonal, P31, a = 13.945(2) Å, c = 30.011(6) Å, V = 5054(2) Å3, Z = 6, dc = 1.401 gcm—1; Rc = 0.0494. 相似文献
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Nest‐shaped cluster [CuBr(bpy)2][MoOS3Cu3Br2(bpy)] was synthesized by the treatment of (NH4)2 MOO2S2, CuBr and Et4NBr with bpy (2,2′‐bipyridyl) in CH3CN. Its structure has been characterized by X‐ray diffraction; monoclinic, space group P21/n ‐ with a = l.0092(4), b = 2.6347(7), c = 1.4087(3) nm, β = 91.744(9)°, V = 3.7438 nm3, Z=4, and final R = 0.051, Rw = 0.053. It consists of two parts: nest‐shaped structural unit [MoOS3Cu3Br2(bpy)] and complex ion [CuBr(bpy)2]+. We determined its third‐order nonlinear optical (NLO) properties with a 7‐ns pulsed laser at 532 nm. The duster exhibits strong NLO refractive behavior, its third‐order susceptibility χ(3) was calculated to be 2.7 · 10?11 esu in a 7.8 · 10?4 g/cm3 DMF solution. The value is comparable to those of inorganic dusters. 相似文献
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By reaction of GeI4, [N(nBu)4]I as iodide donor, and [NMe(nBu)3][N(Tf)2] as ionic liquid, reddish‐black, plate‐like shaped crystals are obtained. X‐ray diffraction analysis of single crystals resulted in the compositions ;alpha;‐[NMe(nBu)3](GeI4)I (Pbca; a = 1495.4(3) pm; b = 1940.6(4) pm; c = 3643.2(7) pm; Z = 16) and β‐[NMe(nBu)3](GeI4)I (Pn; a = 1141.5(2) pm; b = 953.6(2) pm; c = 1208.9(2) pm; β = 100.8(1)°; Z = 2). Depending on the reaction temperature, the one or other compound is formed selectively. In addition, the reaction of GeI4 and [N(nBu)4]I, using [ImMe(nBu)][BF4] (Im = imidazole) as ionic liquid, resulted in the crystallization of [ImMe(nBu)][N(nBu)4](GeI4)3I2 (P21/c; a = 1641.2(3) pm; b = 1903.0(4) pm; c = 1867.7(4) pm; β = 92.0(1)°; Z = 4). The anionic network of all three compounds is established by molecular germanium(IV)iodide, which is bridged by iodide anions. The different connectivity of (GeI4–I–) networks is attributed to the flexibility of I– regarding its coordination and bond length. Here, a [3+1]‐, 4‐ and 5‐fold coordination is first observed in the pseudo‐ternary system M/Ge/I (M: cation). 相似文献
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以1,2-反式-二(4-吡啶基)乙烯桥连卤化铜分别得到配合物[Cu2(bpe)Cl 2] n (1), [Cu2(bpe)Br2] n (2) 和 [Cu2(bpe)I2] n (3)。通过X-射线单晶衍射法对配合物1的结构进行了研究,晶体学数据:单斜晶系, P 2(1)/c空间群, a = 0.3788(8) nm, b = 1.5059(3) nm, c = 1.0875(2)nm, β = 96.262(4) °, V = 616.5(2)Å3, Z = 2, S = 1.002,最终残差因子( I >2 σ ( I )) R 1 = 0.0288, wR 2 = 0.0579,对于全部数据 R 1 = 0.0509, wR 2 = 0.0615。元素分析及红外光谱分析表明,该类配合物为同晶化合物。另外,通过热重分析对配合物的热稳定性进行了研究。 相似文献
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Single crystals of two new modifications of [P(C6H5)4]2[Cu2I4] were obtained by reaction of granulated copper with iodine and [P(C6H5)4]I in dry acetone under nitrogen atmosphere. They crystallise monoclinically, space group P21/n (No. 14), a = 11.550(6), b = 7.236(2), c = 27.232(13) Å, β = 98.13(3)°, V = 2253(2) Å3, and Z = 2 ([P(C6H5)4]2[Cu2I4]-C), and space group Cc (No. 9), a = 17.133(5), b = 15.941(5), c = 18.762 (6) Å, β = 114.02(1)°, V = 4681(3) Å3, and Z = 4 ([P(C6H5)4]2[Cu2I4]-D), respectively. In these compounds the [CuI2]? anions form dimers di-μ-iodo-diiodocuprate(I), which are either planar ( C ) or folded ( D ). 相似文献
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IntroductionRecentlywehaveinvestigatedthestructuralchemistryofanumberofdi ortri organotinheteroaromaticcarboxyl ates.1 5Thesestudieshaveshownthatthestructureoforgan otinheteroaromaticcarboxylatesisdependentonboththena tureofthealkylorarylsubstituentboundtothetinatomandthetypeofcarboxylateligand .Inparticular,majorstructuralvariationsareobservedwhencarboxylateligandcontainsanadditionaldonoratom ,suchasapyridineNatom ,availableforcoordinationtotheSnatom .1 3,5 8Wehavenowturnedtothemonoorganotin… 相似文献