共查询到20条相似文献,搜索用时 31 毫秒
1.
Liu L Zakharov LN Golen JA Rheingold AL Watson WH Hanna TA 《Inorganic chemistry》2006,45(10):4247-4260
We report a series of calix[4]arene Mo(VI) dioxo complexes M2RC4MoO2 (M = alkali metal, R = H or Bu(t)) that were fully characterized by NMR, X-ray, IR, UV/vis, and elemental analysis. Molybdocalix[4]arene structures can be controlled via lower rim deprotonation, groups at para positions of calix[4]arene, and alkali metal counterions. Mono deprotonation at the lower rim leads to calix[4]arene Mo(VI) monooxo complexes RC4MoO (R = H, Bu(t), or allyl), and full deprotonation gives rise to calix[4]arene Mo(VI) dioxo complexes. Structural studies indicate that HC4 Mo(VI) dioxo complexes easily form polymeric structures via cation-pi interaction and coordination between different calixarene units. However, Bu(t)C4 Mo(VI) dioxo complexes tend to form dimers or tetramers due to steric hindrance of the tert-butyl groups at para positions in calixarene. The structures of the reduced side products A and C were determined by X-ray diffraction studies. The mechanism of RC4MoO formation from the reaction of calixarene monoanions with MoO2Cl2 appears to include the addition of a calixarene -OH group across a Mo=O bond. 相似文献
2.
η^5-RO~2CC~5H~4(CO)~3MNa与R^1HgCl,R^1=Me, Et, Ph)可发生一种非预期的金属键形成反应, 生成[η^5-RO~2CC~5H~4(CO)~3M]~2Hg(R=Me,Et;M=Cr,Mo,W)。对反应中间物η^5-EtO~2CC~5H~4(CO)~3MoHgPh的研究表明: 反应是按缩合及对称化两步机理进行的。(R=Et,M=Mo)属三斜晶系, 空间群P-1。a=0.6333(1), b=0.7712(1), c=1.4204(4)nm; a=77.31(1),β=74.51(2), γ=68.72(1)^°; V=0.61714nm^3;Z=1;D~x=2.246g/cm^3;R=0.044。 相似文献
3.
A new method for the synthesis of unsymmetrical calix[4]arenes is described which involves the reaction of a diyne with a bis-carbene complex of chromium. This synthesis of calixarenes is unique in that it involves the formation of two of the four benzene rings of the calixarene and the macrocyclic ring of the calixarene in the same step. Thus, two of the four benzene rings of the calixarene are identical, but the other two rings may each be different, giving a general method for the synthesis of calixarenes in which there are either two or three differently substituted benzene rings. This protocol gives access to a large family of unsymmetrical calixarenes by the proper choice of arene substitution in the starting diyne and the starting carbene complex. Nine examples are presented in which the yields in the key triple annulation step range from 22 to 41%. The overall yields of calixarenes from commercially available starting materials compare favorably with those from existing methods for the synthesis of unsymmetrical calix[4]arenes. 相似文献
4.
Virginie Comte Olivier Blacque Claude Moïse Marek M. Kubicki 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):721-724
Ring substituted (R=tBu, SiMe3) metallocene dichlorides undergo a nucleophilic substitution on one of the two rings upon the action of LiPPh2M'(CO)x salts with the formation of chloro-hydrido complexes [C5H3(R)PPh2M'(CO)x](C5H4R)M(H)Cl. Their UV irradiation leads to the chloro-bridged M(μ-Cl)M' separable diastereoisomers. Use of the ansa-metal-locene dichlorides [Me2X(C5H4)2MCl2] (X=Si or C) allowed the access to the new bridging system [M(μ-PPh2, μ-Cl)M′] (M=Mo, W ; M'=W). 相似文献
5.
Sándor Kunsági-Máté Kornélia Szabó Előd L. Szabó István Bitter Géza Nagy László Kollár 《Supramolecular chemistry》2013,25(3):245-250
The π–π interaction-based inclusion complexation of calix[6]arene hexasulfonate as host with neutral aromatic guest molecules was studied in aqueous media. To vary the distribution of electron density on the guest's aromatic rings, the phenol parent compound was substituted in the para- or ortho- positions with CH3 group. To study the interaction between calixarene and the guests, PL, DSC and quantum-chemical methods were used. The results indicate 1:1 stoichiometry of the formed host-guest complexes. Although the enthalpy change during complex formation of calixarene with p- or o-cresol are the same, the Gibbs free energy change is significantly higher in the case of calixarene—o-cresol complexes. This property is due to the unexpected entropy change during the complex formation. Using molecular dynamic calculations, a guest-induced redistribution of the electron density on the calixarene rings, followed by the restructuring of the solvent molecules was identified as a background of this unexpected entropy change at molecular level. 相似文献
6.
Santra BK Chen JL Sarkar B Liu CW 《Dalton transactions (Cambridge, England : 2003)》2008,(17):2270-2276
A neutral selenium donor ligand, [CpFe(CO)(2)P(Se)(OR)(2)] is used for the construction of Cu(I) and Ag(I) complexes with a well-defined coordination environment. Four clusters [M{CpFe(CO)(2)P(Se)(OR)(2)}(3)](PF(6)), (where M = Cu, R = (n)Pr, ; R = (i)Pr, and M = Ag, R = (n)Pr, ; R = (i)Pr, ) are isolated from the reaction of [M(CH(3)CN)(4)(PF(6))] (where M = Cu or Ag) and [CpFe(CO)(2)P(Se)(OR)(2)] in a molar ratio of 1 : 3 in acetonitrile at 0 degrees C. The reaction of [CpFe(CO)(2)P(Se)(O(i)Pr)(2)] with cuprous halides in acetone produce two mixed-metal, Cu(I)(2)Fe(II)(2) clusters, [Cu(mu-X) {CpFe(CO)(2)P(Se)(O(i)Pr)(2)}](2) (X = Cl, ; Br, ). All six clusters have been fully characterized spectroscopically ((1)H, (13)C, (31)P, and (77)Se NMR, IR), and by elemental analyses. X-Ray crystal structures of and consist of discrete cationic clusters in which three iron-selenophosphito fragments are linked to the central copper or silver atom via selenium atoms. Both clusters and crystallize in the noncentrosymmetric, hexagonal space group P6[combining macron]2c. The coordination geometry around the copper or silver atom is perfect trigonal-planar with Cu-Se and Ag-Se distances, 2.3505(7) and 2.5581(7) A, respectively. X-Ray crystallography also reveals that each copper center in neutral heterometallic clusters and is trigonally coordinated to two halide ions and a selenium atom from the selenophosphito-iron moiety. The structures can also be delineated as a dimeric unit which is generated by an inversion center and has a Cu(2)X(2) parallelogram core. The dihedral angle between the Cu(2)X(2) plane and the plane composed of Cp ring is found to be 24.62 and 84.58 degrees for compound and , respectively. Hence the faces of two opposite Cp rings are oriented almost perpendicular to the Cu(2)X(2) plane in , but are close to be parallel in . This is the first report of the coordination chemistry of the anionic selenophosphito moiety [(RO)(2)PSe](-), the conjugated base of a secondary phosphine selenide, which acts as a bridging ligand with P-coordination on iron and Se-coordination to copper or silver. 相似文献
7.
1INTRODUCTIONRecentresearchonaseriesofdinuclearmolybdenum(0)carbonylcomplexescontain ingthiolato bridgeshasledtotheconclusion... 相似文献
8.
D. Matt S. Steyer L. Allouche A. Louati A. Hamlil C. Strehler M. Neuburger 《Journal of Molecular Structure》2005,740(1-3):53-60
We have recently described the electrochemical oxidation of 5,11,17,23-tetra-tert-butyl-25, 26-bis(diphenylphosphinoylmethoxy)-27,28-dihydroxycalix[4]arene into the corresponding diquinone 1. The solid state structure of 1 has now been determined by a single crystal X-ray diffraction study. Diquinone 1 crystallizes in the monoclinic space group with a=10.3507(12), b=25.219(4), c=20.2315(14) Å, β=101.166(8)°, V=5181.1(10) Å3, Z=4, and Dx=1.273 g cm−3. The calixarene skeleton adopts a partial cone conformation in which one quinone ring is anti-oriented with respect to the other three rings of the calixarene core. A variable temperature NMR study shows that 1 is dynamic in solution, each quinone unit undergoing fast oscillation about the axis that passes through the two meta carbon atoms bonded to the adjacent methylene groups. The motion of the quinone rings was confirmed by 2D NMR experiments. 相似文献
9.
[structure: see text] The first examples of epoxy-p-quinol and diepoxy-p-quinol calixarene derivatives have been obtained by base-promoted direct addition of O(2)(oxygenation) to calixarene phenol rings. The regio- and stereochemistry of these derivatives was determined by 2D NMR studies, in conjunction with MM3 calculations, and X-ray crystallography. Both the oxygenation and the subsequent carbonyl reduction occur with a preferential attack to the less hindered exo face of the calixarene rings. 相似文献
10.
Hsu FF Turk J Shi Y Groisman EA 《Journal of the American Society for Mass Spectrometry》2004,15(1):1-11
Acylphosphatidylglycerol (Acyl-PG), a polar lipid class containing three fatty acyl groups, was isolated from Salmonella bacteria and characterized by tandem quadrupole and quadrupole ion-trap mass spectrometric methods with electrospray ionization. The structural characterization of the acyl-PG with various acyl groups (A-B/C-PG, where A not equal B not equal C) is based on the findings that the carboxylate anions (R(x)CO(2)(-)) arising from sn-2 (R(2)CO(2)(-)) is more abundant than that arising from sn-3' (R(3')CO(2)(-)), which is much more abundant than that arising from sn-1 (R(1)CO(2)(-)). This information provides a simple method for determination of the fatty acyl moieties and their positions in the molecule. The structural identification of the molecule can also be achieved by the findings that the fragment ion reflecting the ketene loss at sn-2 is more prominent than that reflecting the acid loss (i.e., [M - H - R'(2)CH=CO](-) > [M - H - R(2)CO(2)H](-)), while the ion arising from acid loss at sn-1 or sn-3' is, respectively, more abundant than the corresponding ketene loss (i.e., [M - H - R(1)CO(2)H](-) > [M - H - R'(1)CH=CO](-); [M - H - R(3')CO(2)H](-) > [M - H -R'(3')CH=CO](-)). The identity of the acyl moiety at sn-3' can be confirmed by an acyl-glycerophosphate anion observed in the product-ion spectrum obtained with a triple-stage quadrupole (TSQ) instrument, but not in that obtained with an ion-trap mass spectrometer (ITMS). However, the MS(2)-spectrum obtained with an ITMS is featured by the ion series that abundances of [M - H - R'(2)CH=CO - R(3)CO(2)H - 74](-) > [M - H - R'(2)CH=CO - R(1)CO(2)H - 74](-) z.Gt; [M - H - R'(1(or 3'))CH=CO - R(3'(or 1))CO(2)H - 74](-). This information also facilitates structural elucidation of the acyl-PG subclass that contains various acyl substituents. Structural identifications of molecular species having two identical fatty acyl substituents at sn-1, sn-2, or sn-3' or consisting of more than one isomeric structures are also demonstrated. The identities of the minor isomeric species in the molecules can be revealed by the aforementioned structural information arising from the various ion series combined. 相似文献
11.
A family of group 6 transition metal complexes M(C(5)R(5))(CO)(2)(CF) [M = Cr, Mo, W; R = H, Me] with terminal fluoromethylidyne ligands have been synthesized through the reduction of the corresponding trifluoromethyl precursors with potassium graphite or magnesium graphite. They have been characterized spectroscopically and in some cases crystallographically, although the structures show disorder between the CO and CF ligands. The M[triple bond]CF subunit reacts as a triple bond to form cluster complexes containing μ(3)-CF ligands on reaction with Co(2)(CO)(8). Computational (DFT/NBO/NRT) studies on M(C(5)H(5))(CO)(2)(CF) [M = Cr, Mo, W] and the corresponding cationic fragments M(CO)(2)(XY)(+) illustrate significant differences in the metal-ligand bonding between CF and its isoelectronic analogue NO, as well as with its hydrocarbon analogue CH. 相似文献
12.
张 《高等学校化学学报》1999,20(8):1172-1178
利用Co2(CO)8与[Cl3CC(O)OCH2]2的反应合成了以C(O)OCH2CH2OC(O)桥联两个Co3C四面体骨架为特征的新型双四面体簇合物[(CO)9Co3(μ3-C)C(O)OCH2]2(1);1与不同物质的量比的Na[M(CO)3C5H4R](M=Mo,W;R=H,C(O)Me)反应,得到一步交换的产物(CO)9Co3(μ3-C)C(O)OCH2CH2OC(O)(μ3-C)Co2M(CO)8(C5H4R)[M=Mo,R=H(2);M=Mo,R=C(O)Me(3);M=W,R=H(4);M=W,R=C(O)Me(5)]或两步交换的产物[(C5H4R)(CO)8Co2M(μ3-C)C(O)OCH2]2[M=Mo,R=H(6);M=Mo,R=C(O)Me(7);M=W,R=H(8);M=W,R=C(O)Me(9)].5或9分别与Na[Mo(CO)3C5H5]以12的物质的量比反应得到含一个手性四面体骨架(CoMoWC)的(C5H5)(CO)8Co2Mo(μ3-C)C(O)OCH2CH2O·C(O)(μ3-C)CoMoW(CO)7(C5H4C(O)Me)(C5H5)(10)或含两个手性四面体骨架(CoMoWC)的[(C5H5)(C5H4C(O)Me)(CO)7CoMoW(μ3-C)C(O)OCH2]2(11);对化合物1_11进行了CH元素分析、IR和1HNMR等表征.结果表明,在金属交换反应中处于不同簇环境下的Co(CO)3基团反应活性不同.对化合物1进行了晶体X射线衍射分析.化合物1的晶体属单斜晶系,P21/n(#14)空间群,晶胞参数a=0.933 0(2)nm,b=1.519 7(4)nm,c=1.178 3(4)nm,=91.16(2)°,Z=2,F(000)=972.分子结构呈中心对称. 相似文献
13.
种用等瓣置换法,通过M^*[(R-Cp)M^1(CO)~3](R=CO~2Et,COMe;M^*=Na;R=n-Bu;M*=Li)与CpM^2FeCo(CO)~8(μ~3-S)反应,得到六种环戊二烯配体含有较大取代基的含硫四面体手性簇合物(R-Cp)M^1CpM^2Fe(CO)~7(μ~3-S)(I-3:M^1=W,M^2=Mo,R=CO~2Et;Ⅱ:M^1=W,M^2=Mo,R=COMe;Ⅲ:M^1=W,M^2=Mo,R=n-Bu;Ⅳ-2:M^1=Mo,M^2=W,R=CO~2Et;Ⅴ:M^1=Mo,M^2=W,R=COMe;Ⅵ:M^1=Mo,M^2=W,R=n-Bu).通过元素分析,IR,1^H/^1^3CNMR对合成的簇合物结要构进行了表征,并讨论了反应途径。 相似文献
14.
Lothar Weber Marco Meyer Beate Quasdorff 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1571-1574
Reaction of phosphaalkenes RP=C(NMe 2 ) 2 (R = t -Bu, Me 3 Si), featuring an inverse distribution of electron density about the P--C double bond, with Fischer carbene complexes [(CO) 5 M=C(OEt)Ar] (Ar=Ph, 2-MeC 6 H 4 , 2-MeOC 6 H 4 , M = Cr, W) afforded a mixture of complexes [(CO) 5 M{P(R)=C(NMe 2 ) 2 }] and [(CO) 5 M{P(R)=C(OEt)Ar}]. The treatment of phosphaalkene HP=C(NMe 2 ) 2 with compound [(CO) 5 W=C(OEt)(2-MeOC 6 H 4 )] gives rise to the formation of an ( E / Z )-mixture of [(CO) 5 W{P(CH(NMe 2 ) 2 )=C(OEt)(2-MeOC 6 H 4 )}]. 相似文献
15.
1 INTRODUCTION Constructing higher nuclearity clusters with well-defined dimensions and structures provide a rather active field of chemistry with potential applications in areas including nanotechnology, molecular recognition and catalysis[1~4]. A continuing effort has been directed toward developing a better methodology for systematic synthesis of supracluster compounds through molecular design [5,6]. On the basis of extensive investigation on the metal exchange reaction in cluster com… 相似文献
16.
Fuchs A Gudat D Nieger M Schmidt O Sebastian M Nyulaszi L Niecke E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(9):2188-2196
Reaction of the 1,3-diphosphacyclobutane-2,4-diyl-2-ide 1 with chromium or tungsten hexacarbonyl afforded the anionic complexes [cyclo-[P(Mes*)-C(SiMe(3))-P(Mes*)-C(O)-C[M(CO)(5)]]](-) (3 a,b: M=Cr, W) by the formal insertion of CO into the four membered ring. Computational analysis suggests that this reaction proceeds via two intermediates that can be formulated as a cyclic metal acyl and an acyclic ketenyl complex. The anionic complexes 3 a,b further reacted with electrophiles to afford the neutral complexes [cyclo-(P(Mes*)-C(SiMe(3))-P(Mes*)-C(OR)-C[M(CO)(5)])] (4 a,b: M=Cr, W, R=Me; 5, 6: M=Cr, R=SiMe(3), H). All products were characterized by standard spectroscopic (NMR and MS) techniques, and 4 a,b further by extensive one- and two-dimensional multinuclear ((1)H, (13)C, (31)P, (183)W) NMR studies. From these investigations, an unequivocal assignment of chemical shifts and coupling constants was derived, confirming unusually large shielding for the formal carbenic carbon atoms which exceed even those in complexes of imidazoyl carbenes. Single-crystal X-ray diffraction analyses of 3 a, 4 a,b, and 5 revealed that all of these compounds contain planar P(2)C(3) rings. The phosphorus atoms are slightly pyramidal, and the carbon-metal distances (C-Cr 218 pm, C-W 230 pm) suggest low bond orders. Comparison of the structural parameters of 3 a with those of the O-substitution products 4 a, 5 revealed substantial changes in endocyclic P-C bond lengths and the degree of pyramidal character of bonding at the phosphorus atoms. In line with the spectroscopic and computational results, these effects were interpreted in terms of a considerable reorganization of pi electrons in the ring, which induces a substantial degree of aromatic character in the neutral complexes 4-6. 相似文献
17.
对苯二甲酰双环戊烯基锡钼(钨)异多核金属配合物的合成与晶体结构 总被引:1,自引:0,他引:1
通过对苯二甲酰双环戊二烯基三羰基钼(钨)负离子与有机锡的反应,合成了 一系列的对苯二甲酰双环戊二烯基锡钼(钨)异多核金属配合物,并用IR,~1H NMR和元素分析对其进行了表征。结果表明,环戊二烯上的拉电子取代基极大地减 弱金属负离子的亲核性,对苯二甲酰双环戊二烯基三羰基钼(钨)负离子与 R_2SnCl_2(R = Ph, Me, Et)反应时,仅有一个氯原子被金属负离子所取代。用X射 线单晶衍射测定了化合物{p-[(Ph_3Sn)(CO)_3MoC_5H_4-C(O)]_2C_6H_4}的晶体结 构。该晶体为单斜晶系,空间群为C2/c,晶胞参数为:a = 3.4209(10) nm, b = 1.1329(3) nm, c = 1.4214(4) nm, β = 104.466(5) °, V = 5.334(3) nm~3, Z = 4, R = 0.033。两个SnMo结构单元处于桥连苯基的反位。 相似文献
18.
A mechanistic study of diacyl glycerophosphoethanolamine fragmentation under low energy collision-activated dissociation with electrospray ionization tandem mass spectrometry is reported. The fragmentation pathways leading to the formation of carboxylate anions (RxCO2-) (x = 1, 2) and the formation of the ions representing neutral loss of ketene ([M - H - Rx'CH=C=O]-) are charge-driven processes, which are governed by the gas-phase basicity and the steric configuration of the molecules. The fragmentation pathway for the formation of the [M - H - RxCO2H]- ions, reflecting neutral loss of fatty acid, is a charge-remote process, which involves the participation of the hydrogens at C-1 and C-2 of the glycerol, resulting in [M - H - R2CO2H]- > [M - H - R1CO2H]-. The preferential formations of R2CO2- > R1CO2-, and of [M - H - R2'CH=C=O]- > [M - H - R1'CH=C=O]- are attributed to the findings that charge-driven processes are sterically more favorable at sn-2. The observation of the abundance of [M - H - Rx'CH=C=O]- > [M - H - RxCO2H]- is attributed to the fact that the [M - H]- ions of GPE are basic precursor ions, which undergo preferential loss of ketene than loss of acid. The major pathway for the formation of RxCO2- ions arises from the nucleophilic attack of the anionic charge site of the phosphate on the C-1 or C-2 of the glycerol to render a charge transfer. The sterically more favorable attack on the C-2 than C-2 of the glycerol results in the abundance of R2CO2- > R1CO2-. These features of tandem spectra readily identify and locate the fatty acid substituents of GPE in the glycerol backbone. 相似文献
19.
Adams CJ Bartlett IM Boonyuen S Connelly NG Harding DJ Hayward OD McInnes EJ Orpen AG Quayle MJ Rieger PH 《Dalton transactions (Cambridge, England : 2003)》2006,(28):3466-3477
Reduction of [M(CO)2(eta-RC[triple bond]CR')Tp']X {Tp' = hydrotris(3,5-dimethylpyrazolyl)borate, M = Mo, X = [PF6]-, R = R' = Ph, C6H4OMe-4 or Me; R = Ph, R' = H; M = W, X = [BF4]-, R = R' = Ph or Me; R = Ph, R' = H} with [Co(eta-C5H5)2] gave paramagnetic [M(CO)2(eta-RC[triple bond]CR')Tp'], characterised by IR and ESR spectroscopy. X-Ray structural studies on the redox pair [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'] and [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'][PF6] showed that oxidation is accompanied by a lengthening of the C[triple bond]C bond and shortening of the Mo-C(alkyne) bonds, consistent with removal of an electron from an orbital antibonding with respect to the Mo-alkyne bond, and with conversion of the alkyne from a three- to a four-electron donor. Reduction of [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'][PF6] with [Co(eta-C5H5)2] in CH2Cl2 gives [MoCl(CO)(eta-MeC[triple bond]CMe)Tp'], via nitrile substitution in [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'], whereas a similar reaction with [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']+ (M = Mo or W) gives the phosphite-containing radicals [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']. ESR spectroscopic studies and DFT calculations on [M(CO)L(eta-MeC[triple bond]CMe)Tp'] {M = Mo or W, L = CO or P(OCH2)3CEt} show the SOMO of the neutral d5 species (the LUMO of the d4 cations) to be largely d(yz) in character although much more delocalised in the W complexes. Non-coincidence effects between the g and metal hyperfine matrices in the Mo spectra indicate hybridisation of the metal d-orbitals in the SOMO, consistent with a rotation of the coordinated alkyne about the M-C2 axis. 相似文献
20.
CrystalStructureofCalix[4](dioxo)crown-6Acetonitrile(1:3)InclusionComplexZHONGZhen-Lin;CHENYuan-Yin;LUXue-Ran(DepartmentofChe... 相似文献