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1.
SynthesisandCrystalStructureof[(n-Bu)_4N]_2[Mo_4O_(10)(OC_(10)H_6O)_2(OCH_3)_2]¥LuXiao-Ming;ZhuHui-Ju;YangNing;LiuShun-Cheng;JinX?..  相似文献   

2.
1 INTRODUCTIONThefirstpolyhedralruthenaboraneisstructurallytypifiedbythecompound〔(PPh3)2RuB10H8(OEt)2〕in1984〔1〕,whichisobtainedin40%yieldbythereactionoftheclosodecaboraneanionB10H102-with〔RuCl2(PPh3)3〕inethanol/chloroformsolution.Researchershavesy…  相似文献   

3.
MagneticPropertiesofPhenoxy-BridgedBinuclearIron-ThiolatoComplexesandStructureof(Et_4N)_2[Fe_2(o-OC_6H_4S)_2(o-OC_6H_4SH)_2]XIEXi?..  相似文献   

4.
SynthesisandStructureofPropionate-bridgedMixed-metalClusterCompound:〔MoW_2O_2(O_2CC_2H_5)_6(H_2O)_3〕ZnBr_4·4H_2O¥LiuHuang;XuLi;Hua...  相似文献   

5.
SynthesesandCharacterizationsof(η~5-C_5H_5)MoFeCo(CO)_8(μ_3-S)and(η~5-C_5H_5)_2Mo_2Fe(CO)_7(μ_3-S):X-rayCrystalStructureof(η~5-C_5H_...  相似文献   

6.
SynthesisandCrystalStructureof[Na(DB18C6)(H_2O)_2]_2Mo_6O_(19)·3DMF·2CH_3OHLuXiao-Ming;ZhaoYa-Ping;QuEr-Ling;XiaoLing-Mei;LiuShu...  相似文献   

7.
(n—C4H9)4N2(OC14H8O2)Mo4O10(OCH3)2的合成和晶体结构   总被引:4,自引:1,他引:4  
为探讨钼多酸根阴离子在有机化学反应中的催化机理,用菲醌作底物合成了(n-C4H9)4N)2(OC14H8O)2Mo4O10O10(OCH3)2)配合物,X射线单晶结构分析表明,该晶体属单斜晶系,空间群P21/c,a=1.3149(5)nm,b=1.8666(8)nm,c=1.8903(3)nm,β=104.06(3)Z=2.收集到独立衍射点3505个,其中1382个为可观测点,最终一致性因子R=0  相似文献   

8.
1 INTRODUCTIONDimolybdenumalkynecomplexes〔Mo2(μR1C≡CR2)(CO)4(η5C5H5)2〕canreactwithavarietyofreagentssuchasphosphines,thiols,elementalsulfur,Ru3(CO)12andCo2(CO)8〔1-4〕.Intheproductsthealkyneligandisusuallyretained.Sometimes,alkynescissionoccurs.Being…  相似文献   

9.
在不同条件下合成了[Co(phen)mXp]Y1·nH2O型配合物,(m=1,2;p=1,2;1=1-3;n=0-4;phen=邻菲绕啉;X=Cl-,H2O,酒石酸(tart),甘氨酸(gly),α-皮可林酸(pic).DL-两氨酸(ala),L-亮氨酸(leu),L-脯氨酸(pro);Y=Cl-,]并进行了元素分析,热重分析,电子光谱,红外光谱和磁化率测定,计算它们的10Dq和B值.X-ray单晶衍射实验证明:[Co(Phen)2(H2O)2](NO3)3·2H2O,[Co(Phen)2(gly)]Cl2·4H2O均为顺式结构.[Co(Phen)(ala)2]Cl·3H2O,[Co(Phen)(pro)2]ClO4·4/3H2O均为trans(N)结构.在[Co(phen)2X2](n+)型配合物中,X反位的键长均长于顺位键长,其反位效应的顺序为:Cl->羧基,NH2>H2O。  相似文献   

10.
SynthesisandStructureoftheHexanuclearDiazenido-oxomolybdate[(n-C_4H_9)_4N]_3[Mo_6O_(18)(N_2C_6H_4-p-NO_2)]LiHai-Lian;YouXiao-Zeng;...  相似文献   

11.
12.
Reactions between closo-1,2-C(2)B(8)H(10) (1) and amines of general formulation R(1)R(2)NH (where R(1), R(2) = H, H; Me, H; t-Bu, H and Et, Et) resulted in a straightforward cluster expansion and formation of the 11-vertex arachno-azadicarbaboranes of the 1,1-R(1),R(2-)1,6,9-NC(2)B(8)H(11) (2) cluster constitution (where R(1), R(2) = H, H 2a; Me, H 2b; t-Bu, H 2c and Et, Et 2d) in yields 10-75%, depending on the nature of the amine used. The reactions are the first example of a direct closo to arachno transformation in the area of cluster-boron compounds. Compounds 2b and 2c were isolated in two isomeric forms anti- and syn- that differ in the positioning of the t-Bu substituent with respect to the bridging hydrogen site. Deprotonation of compounds 2 generally leads to removal of the bridging proton and formation of the [1,1-R(1),R(2-)1,6,9-NC(2)B(8)H(11)](-) (2-) anions that, in the case of the monoalkylated Me and t-Bu derivatives, adopt only an anti configuration. The structure of anti-2c was determined by X-ray diffraction analysis and the geometries of the parent compound and the corresponding syn and anti isomers were optimised at the RMP2/6-31G* level. The composition of all compounds is consistent with the results of mass spectrometry and multinuclear ((1)H and (11)B) spectroscopy complemented by two-dimensional [(11)B-(11)B]-COSY and (1)H{(11)B(selective)} NMR measurements. Experimental (11)B chemical shifts generally show acceptable agreement with theoretical values calculated by GIAO methods, in particular at GIAO-MP2/II, where possible.  相似文献   

13.
The closo-[B12H12-n(OH)n]2- (n = 1-4) ions have been synthesized by the reaction of cesium dodecahydro-closo-dodecaborate(2-), Cs21, with aqueous sulfuric acid. Variation of the reaction temperature, time, and acid concentration results in the stepwise introduction of from one to four hydroxyl groups. Each individual hydroxylation step proceeds regioselectively, affording only one isomer per step. Further substitution of the hydroxylated cluster preferentially takes place at a B-H vertex meta to a B-OH vertex. The closo-[B12H12-n(OH)n]2- (n = 1-4) species, designated 2-5, respectively, are characterized by one- and two-dimensional 11B NMR spectroscopy, IR spectroscopy, and high-resolution fast atom bombardment (FAB) mass spectrometry. A rationale that qualitatively explains the influence of the hydroxyl group on the chemical shifts of the individual boron vertices is developed. Furthermore, the solid state structures of closo-[B12H11(OH)]2-, 2, and closo-1,7-[B12H10(OH)2]2-,3, are determined by X-ray diffraction. Crystallographic data are as follows: For [MePPh3](2)2, monoclinic, space group P2(1)/n, a = 890.1(5) pm, b = 1814(1) pm, c = 1270.5(7) pm, beta = 101.66(2) degrees, Z = 2, R = 0.055; for [MePPh3](2)3, monoclinic, space group P2(1)/n, a = 887.6(4) pm, b = 1847.2(8) pm, c = 1271.1(5) pm, beta = 101.17(1) degrees, Z = 2, R = 0.065. In addition, synthetic routes to O-derivatized species of the anions 2-5 such as closo-[B12H11(OTiCpCl2)]2-, 7, closo-1,7-[B12H10(OTiCpCl2)2]2-, 8, closo-1,7,9-[B12H9(OTiCpCl2)3]2-, 9, closo-[B12H11(OCONHPh)]2-, 10, and closo-1,7-[B12H10(OSO2Me)2]2-, 11, are described. The crystal structures of 7 and 11 are determined by single-crystal X-ray diffraction. Crystallographic data are as follows: For [MePPh3](2)7, monoclinic, space group Cc, a = 2530.5(2) pm, b = 1653.3(1) pm, c = 1281.3(1) pm, beta = 118.79(2) degrees, Z = 4, R = 0.085; for [HPy](2)11, monoclinic, space group P2(1)/n, a = 1550.9(8) pm, b = 993.1(5) pm, c = 1726.5(9) pm, beta = 112.36(2) degrees, Z = 4, R = 0.061.  相似文献   

14.
The stirring of [ortho-(HC[triple bond]C)-C(5)H(4)N] with [nido-B(10)H(14)] in benzene affords [6,9-{ortho-(HC[triple bond]C)-C(5)H(4)N}(2)-arachno-B(10)H(12)] 1 in 93% yield. In the solid state, 1 has an extended complex three-dimensional structure involving intramolecular dihydrogen bonding, which accounts for its low solubility. Thermolysis of 1 gives the known [1-(ortho-C(5)H(4)N)-1,2-closo-C(2)B(10)H(11)] 2 (13%), together with new [micro-5(N),6(C)-(NC(5)H(4)-ortho-CH(2))-nido-6-CB(9)H(10)] 3 (0.4%), [micro-7(C),8(N)-(NC(5)H(4)-ortho-CH(2))-nido-7-CB(10)H(11)] (0.4%) , 4 binuclear [endo-6'-(closo-1,2-C(2)B(10)H(10))-micro-(1(C),exo-6'(N))-(ortho-C(5)H(4)N)-micro-(exo-8'(C),exo-9'(N))-(ortho-(CH(2)CH(2))-C(5)H(4)N)-arachno-B(10)H(10)] (0.5%) 5, and [exo-6(C)-endo-6(N)-(ortho-(CH[double bond]CH)-C(5)H(4)N)-exo-9(N)-(ortho-(HC[triple bond]C)-C(5)H(4)N)-arachno-B(10)H(11)] 6. An improved solvent-free route to 2 is also presented. This set of compounds features an increasing cluster incorporation of the ethynyl moiety, initially by an effective internal hydroboration, affording an arachno to nido and then a nido to arachno:closo sequence of cluster geometry. An alternative low-temperature route to internal hydroboration is demonstrated in the room temperature reaction of [closo-B(11)H(11)][N(n)Bu(4)](2) with CF(3)COOH and [ortho-(HC[triple bond]C)-C(5)H(4)N], which gives [micro-1(C),2(B)-[ortho-C(5)H(4)N-CH(2)]-closo-1-CB(11)H(10)] 7 (40%) in which one carbon atom is incorporated into the cluster; a similar reaction with [ortho-(N[triple bond]C)-C(5)H(4)N] affords [N(n)Bu(4)][7-(ortho-N[triple bond]C-C(5)H(4)N)-nido-B(11)H(12)], 8 (68%) and stirring [ortho-(N[triple bond]C)-C(5)H(4)N] with [nido-B(10)H(14)] quantitatively affords the cyano analogue of 1, [6,9-{ortho-(N[triple bond]C)-C(5)H(4)N}(2)-arachno-B(10)H(12)] 9. All compounds were characterised by single-crystal X-ray diffraction analysis and NMR spectroscopy.  相似文献   

15.
Three dinuclear copper(i) complexes with the formula [Cu(2)(mu-X)(2)(1,2-(P(i)Pr(2))(2)-1,2-C(2)B(10)H(10))(2)] (X = Cl (), Br (), I ()) containing the closo carborane diphosphine ligand 1,2-(P(i)Pr(2))(2)-1,2-C(2)B(10)H(10) have been prepared and characterized by elemental analysis, FT-IR and X-ray structure determination. The X-ray structure analyses revealed that the three complexes were isostructural and crystallized in the monoclinic system and space group C2/m. The carborane cage ligand was coordinated bidentately to the Cu(i) center through its two phosphorus atoms, and the coordination geometry around each copper atom was distorted tetrahedral. Two halogen atoms bridged the metal centers forming a dimer structure [Cu(2)(mu-X)(2)(1,2-(P(i)Pr(2))(2)-1,2-C(2)B(10)H(10))(2)], which were linked into 2D supramolecular networks through novel C-HH-B dihydrogen bonding interactions.  相似文献   

16.
A new family of photoluminescent neutral and anionic di-carboranyl and tetra-carboranyl derivatives have been synthesized and characterized. The reaction of α,α'-bis(3,5-bis(bromomethyl)phenoxy-m-xylene with 4 equiv. of the monolithium salt of 1-Ph-1,2-C(2)B(10)H(11) or 1-Me-1,2-C(2)B(10)H(11) gives the neutral tetracarboranyl-functionalized aryl ether derivatives closo-1 and closo-2, respectively. The addition of the monolithium salt of 1-Ph-1,2-closo-C(2)B(10)H(11) to α,α,'-dibromo-m-xylene or 2,6-dibromomethyl-pyridine gives the corresponding di-carboranyl derivatives closo-3 and closo-4. These compounds, which contain four or two closo clusters, were degraded using the classical method, KOH in EtOH, affording the corresponding nido species, which were isolated as potassium or tetramethylammonium salts. All the compounds were characterized by IR, (1)H, (11)B and (13)C NMR spectroscopy, and the crystal structure of closo-3 was analysed by X-ray diffraction. The carboranyl fragments are bonded through CH(2) units to different organic moieties, and their influence on the photoluminescent properties of the final molecules has been studied. All the closo- and nido-carborane derivatives exhibit a blue emission under ultraviolet excitation at room temperature in different solvents. The fluorescence properties of these closo and nido-derivatives depend on the substituent (Ph or Me) bonded to the C(cluster), the solvent polarity, and the organic unit bearing the carborane clusters (benzene or pyridine). In the case of nido-derivatives, an important effect of the cation is also observed.  相似文献   

17.
It has been shown by IR and NMR spectroscopy that cyclic trimeric perfluoro-o-phenylenemercury (o-C6F4-Hg)3 (1) is capable of binding closo-[B10H10]2- and closo-[B12H12]2- anions to form complexes [[(o-C6F4Hg)3](B10-H10)]2- (2), [[(o-C6F4Hg)3]2(B10H10)]2-(3), [[(o-C6F4Hg)3](B12H12)]2- (4), and [[(o-C6F4Hg)3]2(B12H12)]2- (5). According to IR data, the bonding of the [B10H10]2- and [B12H12]2- ions to the macrocycle in these complexes is accomplished through the formation of B-H-Hg bridges. Complexes 2, 3, and 5 have been isolated in analytically pure form and have been characterized by spectroscopic means. X-ray diffraction studies of 3 and 5 have revealed that these compounds have unusual sandwich structures, in which the polyhedral di-anion is located between the planes of two molecules of 1 and is bonded to each of them through two types of B-H-Hg bridges. One type is the simultaneous coordination of a B-H group to all three Hg atoms of the macrocycle. The other type is the coordination of a B-H group to a single Hg atom of the cycle. According to X-ray diffraction data, complex 2 has an analogous but half-sandwich structure. The obtained complexes 2-5 are quite stable; their stability constants in THF/acetone (1:1) at 20 degrees C have been determined as 1.0 x 10(2)Lmol(-1), 2.6 x 10(3)L(2)mol(2), 0.7 x 10(2)Lmol(-1), and 0.98 x 10(3)L(2)mol(-2), respectively.  相似文献   

18.
We propose a mechanism for the cage-opening reaction of a four atoms shared closo/closo B20H16 (1) with MeCN to a face shared closo/nido macropolyhedron B20H16(MeCN)2 (4) through a diamond-square-diamond rearrangement. Even though only one isomer of the product has been reported experimentally, our computational studies at the B3LYP/6-31G* level predict the possibility of the formation of the other isomers. Depending upon the position of the attack of the MeCN ligand on the polyhedral skeleton, different products are formed. The energetics of the reactions of B20H16 with Me2S and H2O are comparable.  相似文献   

19.
The icosahedral dicarboranes and their decapitated anion, 1-R'-1,2-C(2)B(10)H(10) (closo) and [7-R'-7,8-C(2)B(9)H(10)](-) (nido), exert a distict influence at the alpha position of substituents attached to the cage carbon atom. The closo fragment is electron-withdrawing while the nido anion is electron-releasing. These effects are studied by (31)P NMR, phosphorus oxidation, and phosphorus protonation in [7-PR(2)-8-R'-7,8-C(2)B(9)H(10)](-) species. The (31)P NMR chemical shift dependence is related to the R alkyl or aryl nature of [7-PR(2)-8-R'-7,8-C(2)B(9)H(10)](-). No direct relationship to the nature of the R substituent on the nido-carboranylmonphosphine toward oxidation has been found. The basicity of the nido-alkylcarboranylmonophosphines is the highest while the lowest corresponds to the nido-arylcarboranylmonophosphines. Interpretation can be carried out qualitatively by considering the electronic properties of the cluster and the nature of the R groups. The influence of R' is less relevant. Confirmation of the molecular structure of the oxidated and protonated nido-carboranylmonophosphine compounds was obtained by X-ray diffraction analysis of [NBu(4)][7-P(O)Ph(2)-8-Ph-7,8-C(2)B(9)H(10)] and [7-PH((i)Pr)(2)-8-Me-7,8-C(2)B(9)H(10)].  相似文献   

20.
The reaction of alpha,alpha'-bis(3,5-bis(bromomethyl)phenoxy-p-xylene (3) with 4 equiv of the monolithium salt of 1-Ph-1,2-C2B10H11 or 1-Me-1,2-C2B10H11 gave the corresponding neutral carboranyl-functionalized aryl ether derivatives closo-4 and closo-5, respectively. These compounds contain four closo clusters that were degraded using basic conditions with KOH in EtOH, affording the corresponding nido-6 and nido-7 as potassium salts. Nido species were also isolated with tetramethylammonium as cation giving compounds nido-8 and nido-9 in good yield. The potassium salts showed good solubility in water and polar solvents. All these compounds were characterized by 1H, 11B and 13C NMR spectroscopy and UV-vis. The electronic data in different solvents indicated a solvatochromic shift for all compounds and a red shift of the absorption maxima for the nido species with respect to the closo derivatives. These neutral and anionic carboranyl-functionalized aryl ether derivatives represent a new family of high boron content luminescent compounds that show strong fluorescence emission in different solvents at room temperature. This phenomenon is very interesting considering the fact that none of the precursors have such a property. The fluorescence emission depends on the cluster substituent (Ph or Me) and the solvent polarity. Additionally, the fluorescence emission intensity was clearly dependent on the solvent polarity; the closo species showed strongest fluorescence intensities in the non-polar solvents, while anionic species were highly emissive in polar solvents.  相似文献   

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