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Anwar MU Elliott AS Thompson LK Dawe LN 《Dalton transactions (Cambridge, England : 2003)》2011,40(17):4623-4635
Hydrazone ligands modified with benzothiazole and oxime groups produce spin-coupled tetra- (Mn, Ni, Cu), penta- (Co), and hexanuclear (Cu) self-assembled clusters. 相似文献
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Alexander Higelin Ulf Sachs Sarah Keller Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(32):10029-10034
In a new oxidative route, Ag+[Al(ORF)4]? (RF=C(CF3)3) and metallic indium were sonicated in aromatic solvents, such as fluorobenzene (PhF), to give a precipitate of silver metal and highly soluble [In(PhF)n]+ salts (n=2, 3) with the weakly coordinating [Al(ORF)4]? anion in quantitative yield. The In+ salt and the known analogous Ga+[Al(ORF)4]? were used to synthesize a series of homoleptic PR3 phosphane complexes [M(PR3)n]+, that is, the weakly PPh3‐bridged [(Ph3P)3In–(PPh3)–In(PPh3)3]2+ that essentially contains two independent [In(PPh3)3]+ cations or, with increasing bulk of the phosphane, the carbene‐analogous [M(PtBu3)2]+ (M=Ga, In) cations. The MI? P distances are 27 to 29 pm longer for indium, and thus considerably longer than the difference between their tabulated radii (18 pm). The structure, formation, and frontier orbitals of these complexes were investigated by calculations at the BP86/SV(P), B3LYP/def2‐TZVPP, MP2/def2‐TZVPP, and SCS‐MP2/def2‐TZVPP levels. 相似文献
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Dr. Zhengong Meng Dr. Guijun Li Dr. Sze-Chun Yiu Dr. Nianyong Zhu Prof. Dr. Zhen-Qiang Yu Dr. Chi-Wah Leung Prof. Dr. Ian Manners Prof. Dr. Wai-Yeung Wong 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(28):11618-11623
Self-assembly of d8 metal polypyridine systems is a well-established approach for the creation of 1D organometallic assemblies but there are still challenges for the large-scale construction of nanostructured patterns from these building blocks. We describe herein the use of high-throughput nanoimprint lithography (NIL) to direct the self-assembly of the bimetallic complexes [4′-ferrocenyl-(2,2′:6′,2′′-terpyridine)M(OAc)]+(OAc)− (M=Pd or Pt; OAc=acetate). Uniform nanorods are fabricated from the molecular self-organization and evidenced by morphological characterization. More importantly, when top-down NIL is coupled with the bottom-up self-assembly of the organometallic building blocks, regular arrays of nanorods can be accessed and the patterns can be controlled by changing the lithographic stamp, where the mold imposes a confinement effect on the nanorod growth. In addition, patterns consisting of the products formed after pyrolysis are studied. The resulting arrays of ferromagnetic FeM alloy nanorods suggest promising potential for the scalable production of ordered magnetic arrays and fabrication of magnetic bit-patterned media. 相似文献
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The title complexes [M(ImH)4(tfbdc)(H2O)] ( 1 : M=Co; 2 : M=Ni) (ImH=imidazole, tfbdc=2,3,5,6‐tetrafluoroterephthalate) were synthesized by the reaction of M(OAc)2·4H2O, H2tfbdc and ImH in water solution. The complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, cyclic voltammetry and X‐ray single crystal structure analysis. Structural analysis reveals that 1 and 2 possess isostructure: monoclinic, P21/c, Z=4. M(II) ion in complexes 1 and 2 has a distorted octahedral geometry coordinated by one oxygen atom from water, one oxygen atom from tfbdc2? and four nitrogen atoms from ImHs. They are discrete zero‐dimensional molecular complexes. And the adjacent monomeric components are connected by hydrogen bonds to form a supramolecule. Electrochemical properties of the complexes 1 and 2 show that electron transfer of M(II) between M(III) in electrolysis is a quasi‐reversible process. 相似文献
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Reactions of [{M(μ‐Cl)(coe)2}2] (M = Rh, Ir; coe = cis‐cyclooctene) with the secondary phosphane tBu2PH under various molar ratios were investigated. Probably, for kinetic reasons, the reaction behavior of the rhodium species differed from that of the iridium analogue in some instances. During these studies complexes [MCl(tBu2PH)3] [M = Rh ( 1 ), Ir ( 2 )] were isolated, and solution variable‐temperature 31P{1H} NMR studies revealed that these complexes show a conformational rigidity on the NMR time scale. Spectra recorded in the temperature range from 173 to 373 K indicated in each case only one rotamer containing three chemically nonequivalent phosphanes due to the restricted rotation of these ligands about the M–P bonds and the tert‐butyl substituents around the P–C(tBu) bonds, respectively. Compound 1 showed in solution already at room temperature in several solvents a dissociation of a phosphane ligand affording the known complex [{Rh(μ‐Cl)(tBu2PH)2}2] beside the free phosphane. In contrast to these findings, the iridium analogue 2 remained completely unchanged under similar conditions and exhibited, therefore, some kinetic inertness. For a better understanding of the NMR spectroscopic investigations, the molecular structure of 1 in the solid state was confirmed by X‐ray crystallography. 相似文献
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运用密度泛函理论研究了(1,3,5-C3P3H3)M和(1,3,5-C3P3H3)2M (M=Ti,V,Cr)的结构、键合能以及芳香性.结果表明:低自旋的(1,3,5-C3P3H3)M和(1,3,5-C3P3H3)2M基态结构分别具有C3v和D3h对称性.金属与配体间为共价作用,二者之间存在σ、π和σ三种成键方式.V的三明治配合物的解离方式与Ti和Cr的三明治配合物不同,前者为分步解离,后两者则为一步解离.其中(1,3,5-C3P3H3)2Cr(D3h)的第一解离能最大,配合物最稳定.这些三明治和半三明治配合物都具有中心芳香性、内芳香性和外芳香性,且中心芳香性均大于自由配体(1,3,5-C3P3H3)的中心芳香性,芳香性主要贡献来源于π键和金属原子的孤对电子.内芳香性按照Ti、V、Cr的顺序依次增大,且内芳香性明显要大于外芳香性.高自旋的半三明治(1,3,5-C3P3H3)Ti(C3,5A1)与单重态(1,3,5-C3P3H3)Ti (C3v,1A1)相比,配体的变形性增大,稳定性增加,且C平面中心芳香性和内芳香性均增大,但P平面的中心芳香性却降低. 相似文献
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Da-Cheng Li Zeng-Xin Li Jian-Min Dou Da-Qi Wang 《Journal of inclusion phenomena and macrocyclic chemistry》2003,46(1-2):83-88
Two benzo-18-crown-6 (B18-C-6) complexes: [Na(B18-C-6)]2[Pd(SCN)4](H2O)({bf 1}) and [Na(B18-C-6)]2[Pt(SCN)4]...0.5C2H4C12 (2)have been synthesized and characterized by elemental analysis, IR spectrum and X-raydiffraction analysis. The crystal of complex 1 belongs to monoclinic, space group P21/n with cell dimensions, a = 1.0481(3), b = 1.2864 (3), c = 1.7003 (4) nm, = 93.626(4)°, V = 2.2879 (9) nm3, Z = 2, Dcalcd = 1.491 g/cm3, F(000) = 1060, R1 = 0.0562, wR2 = 0.1412 and 2 is triclinic, spacegroup P1 with cell dimensions, a = 0.9581(3), b = 1.2173 (3), = 2.1198 (6) nm, = 79.522(4), = 77.911(4), = 78.617(4)°, V = 2.3442(11) nm3 Z = 2, Dcalcd = 1.626 g/cm3, F(000) = 1154, R1 = 0.0515, wR2 = 0.0612.Two complexes show one-dimensional chain of [Na(B18-C-6)]+ complex cations and [M(SCN)4]2- (M = Pd, Pt) complex anion bridged by Na–O–Na interactions of H2O molecule or Na-O bond of B18-C-6 between adjacent [Na(B18-C-6)]+ units respectively. 相似文献
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Novel Transition‐Metal (M=Cr,Mo, W,Fe) Carbonyl Complexes with Bis(guanidinato)silicon(II) Ligands 下载免费PDF全文
Felix M. Mück Dorit Kloß Johannes A. Baus Dr. Christian Burschka Prof. Dr. Reinhold Tacke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9620-9626
The donor‐stabilized silylene 2 (the first bis(guanidinato)silicon(II ) complex) reacts with the transition‐metal carbonyl complexes [M(CO)6] (M=Cr, Mo, W) to form the respective silylene complexes 7 – 10 . In the reactions with [M(CO)6] (M=Cr, Mo, W), the bis(guanidinato)silicon(II ) complex 2 behaves totally different compared with the analogous bis(amidinato)silicon(II ) complex 1 , which reacts with [M(CO)6] as a nucleophile to replace only one of the six carbonyl groups. In contrast, the reaction of 2 leads to the novel spirocyclic compounds 7 – 9 that contain a four‐membered SiN2C ring and a five‐membered MSiN2C ring with a M?Si and M?N bond (nucleophilic substitution of two carbonyl groups). Compounds 7 – 10 were characterized by elemental analyses (C, H, N), crystal structure analyses, and NMR spectroscopic studies in the solid state and in solution. 相似文献
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Mohammed Benzakour Mohammed Mcharfi Alain Cartier Abdelali Daoudi 《Journal of Molecular Structure》2004,710(1-3):169-174
In view of better understanding interactions of aminoacids and peptides with metallic cations, in the isolated state and in water, the model system glycylglycine–M+ (M=Li, Na) has been studied theoretically. The computations have been performed with the help of the density functional theory (DFT) and the B3LYP functional. The extended basis set was the standard 6-31++G**. In solution we used a recent model of continuum with a multicentric multipole expansion of the charge distribution. Our study shows that low energy complexes with lithium and sodium are rather similar. In the isolated state, the most stable form corresponds to a bidentate complex in which the cation interacts with two oxygen atoms, one from the terminal COOH and one from the amidic carbonyl. In solution, the coordination of the cation in the most stable form is 3, the nitrogen of the end amino group being the third ligand.
The energy range between the lowest energy structure and the highest energy one, in both cases, is slightly reduced under the electrostatic influence of the solvent. 相似文献
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Two new ion-pair complexes [Co(BBP)2]2[Ni(mnt)2]Cl2·4DMF·2H2O(1, BBP =2,6-bis(benzimidazol-2'-yl) pyridine, mnt = maleonitriledithiolate) and [(Py)2CH2][Co(mnt)2]2·4DMF(2) have been synthesized and characterized by elemental analyses, IR spectroscopy,thermogravimetric analyses and single-crystal X-ray diffraction. X-ray diffraction studies show that complex 1 crystallizes in monoclinic, space group P21/c. The crystal of 2 belongs to a triclinic system with space group P1. Due to the hydrogen bonding interactions, anions and cations formed the mixed packing in complex 1 while the anions and cations formed segregated columns in 2. In addition, thermogravimetric analyses of the two complexes are also investigated. 相似文献
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Schoonover JR Zietlow TC Clark DL Heppert JA Chisholm MH Gray HB Sattelberger AP Woodruff WH 《Inorganic chemistry》1996,35(22):6606-6613
Resonance Raman spectra of the cubic metal-halide complexes having the general formula [M(6)X(8)Y(6)](2)(-) (M = Mo or W; X, Y = Cl, Br, or I) are reported. The three totally symmetric fundamental vibrations of these complexes are identified. The extensive mixing of the symmetry coordinates that compose the symmetric normal modes expected in these systems is not observed. Instead the "group-frequency" approximation is valid. Furthermore, the force constants of both the apical and face-bridging metal-halide bonds are insensitive to the identity of either the metal or the halide. Raman spectra of related complexes with methoxy and benzenethiol groups as ligands are reported along with the structural data for [Mo(6)Cl(8)(SPh)(6)][NBu(4)](2). Crystal data for [Mo(6)Cl(8)(SPh)(6)][NBu(4)](2) at -156 degrees C: monoclinic space group P2(1)/c; a = 12.588(3), b = 17.471(5), c = 20.646(2) ?; beta = 118.53(1) degrees, V = 3223.4 ?(3); d(calcd) = 1.664 g cm(-)(3); Z = 2. 相似文献
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Qian Wang Sudip Pan Yan‐Bo Wu Guohai Deng Jian‐Hong Bian Guanjun Wang Lili Zhao Mingfei Zhou Gernot Frenking 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(48):17526-17535
We report the synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)3 (M=Sr, Ba) in low‐temperature Ne matrix. Both complexes are characterized by a D3 symmetric structure involving three equivalent η6‐bound benzene ligands and a closed‐shell singlet electronic ground state. The analysis of the electronic structure shows that the complexes exhibit metal–ligand bonds that are typical for transition metal compounds. The chemical bonds can be explained in terms of weak donation from the π MOs of benzene ligands into the vacant (n?1)d AOs of M and strong backdonation from the occupied (n?1)d AO of M into vacant π* MOs of benzene ligands. The metals in these 20‐electron complexes have 18 effective valence electrons, and, thus, fulfill the 18‐electron rule if only the metal–ligand bonding electrons are counted. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals. 相似文献
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Three heterometallic supramolecular complexes [Cu2(pn)4(Mo(CN)8)·4H2O] (pn = diaminopropane) ( 1 ), [Cu2(pn)4(W(CN)8)·4H2O] ( 2 ) and [Cu2(1,2‐pn)4(H2O) (W(CN)8)·3H2O] ( 3 ) have been synthesized and structurally characterized by single‐crystal X‐ray diffraction studies. Complexes 1 – 3 exhibit three different networks. In 1 , the copper(II) ion is pentacoordinate with a distorted square‐pyramidal arrangement and the network is formed by the incorporation of coordinative linkage between the μ2 bridge of [Mo(CN)8]4– and copper(II) ions and hydrogen‐bonding interactions. In 2 , the copper(II) ion exhibits a distorted square‐pyramidal arrangement and the network is formed by the hydrogen bonded trinuclear complexesof [Cu2(pn)2(W(CN)8)]. In 3 , the copper(II) ions show twodifferent distorted octahedral arrangements. The network structure of 3 is formed by the hydrogen‐bonded complex chains of [Cu2(1,2‐pn)2(W(CN)8)]. 相似文献
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Antokhina T. F. Ignat'eva L. N. Kaidalova T. A. Savchenko N. N. 《Russian Journal of Coordination Chemistry》2003,29(3):157-162
Monoclinic crystals of ammonium hydrofluoride fluoro complexes of zirconium and hafnium (NH4)4M(Zr(Hf))3F17 · 2HF (M = Li, Na) are synthesized and studied. Their unit cell parameters are determined. IR spectra of the synthesized compounds are measured in the range of 350–4000 cm–1. 相似文献