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1.
The syntheses and the X-ray structures of the tetranuclear gold(I) benzamidinate, Au4[PhNC(Ph)NPh]4, and the tetranuclear gold(I) acetamidinate, Au4[PhNC(CH3)NPh]4, clusters are reported. The clusters are produced by the reaction of the sodium salt of an amidine ligand with the gold precursor
Au(THT)Cl in a (1:1) stoichiometry. The average Au...Au distance between adjacent Au(I) atoms is ∼2.9 ?, typical of compounds
having an aurophilic interaction. The four gold atoms are arranged in a square (Au...Au...Au... = 88–91°) in the acetamidinate
and in a distorted square (Au...Au...Au... = 82–97°) in the benzamidinate derivative. Electrochemical oxidation of the tetranuclear
complex Au4[PhNC(Ph)NPh]4 show three reversible waves at 0.87, 1.19, 1.42 V vs. Ag/AgCl at a scan rate of 100 mV/s in CH2Cl2 similar to the three reversible waves seen before from the tetranuclear complexes Au4[ArNC(H)NAr]4, Ar = C6H4-4-OMe, Ar = C6H4-4-Me, and Ar = C6H3-3,5-Cl. A summary of the chemistry of the tetranuclear Au(I) amidinate complexes Au4[ArNC(H)NAr]4, Ar = C6H4-4-OMe, C6H3-3,5-Cl, C6H4-4-Me, C6H4-3-CF3, C6F5, C10H7 also is presented. The tetranuclear clusters Au4[ArNC(H)NAr]4, Ar = C6H4-4-OMe, Ar = C6H4-3-CF3, Ar = C6H4-4-Me and Ar = C6H4-3,5-Cl are the first tetranuclear gold(I) cluster species from group 11 elements to show fluorescence at room temperature.
The lifetimes of the naphthyl and trifluoromethylphenyl complexes are in the millisecond range indicating phosphorescent processes.
Recently it has been shown that Au4[ArNC(H)NAr]4 are very effective catalysts upon calcination for room temperature CO oxidation.
Congratulations to Dieter Fenske, a superb synthetic chemist with exceptional talents in cluster chemistry, on the occasion
of his 65th birthday. 相似文献
2.
[Pd(C6F5)2(CNR)2] (R = Cy, But, p-MeC6H4 (p-Tol)) react with [PdCl2(NCPh)2] to give [Pd2(μ-Cl)2(C6F5)2(CNR)2]. In refluxing benzene insertion of isocyanide into the C6F5Pd bonds occurs only for R = p-Tol, to give a imidoyl bridged polynuclear complex cis-[Pd2 (μ-Cl)2[μ-C(C6F5) = N(Tol-p)]2n]. This complex reacts with (a) Tl(acac) to give [Pd2{μ-C(C6F5) = N(Tol-p)}2(acac)2]; (b) neutral monodentate ligands to afford dimeric complexes [Pd2{μ-C(C6F5) = N(Tol-p)}2Cl2L2] (L = NMe3, py, 4-Me-py, SC4H8), and (c) isocyanides to give insoluble complexes of the same composition which are thought to be polymeric, [(CNR)Cl{μ-C(C6F5) = (p-Tol)}]n (R = p-Tol, Me, But). Thermal decomposition of cis-[Pd2 (μ-Cl)2 [μ-C(C6F5) = N( p-Tol)]2n] gives the diazabutadiene species (p-Tol)NC(C6F5)C(C6F5)N(p-Tol) in high yield. 相似文献
3.
D. P. Domonov S. I. Pechenyuk N. L. Mikhailova A. T. Belyaevskii 《Russian Journal of Inorganic Chemistry》2007,52(7):1027-1032
The thermolysis of the complexes [Co(NH3)6]2C2O4[Cu(C2O4)2]2 (I) and [Co(NH3)6]Cl[Cu(C7H4O3)2] (II) in air and hydrogen at 200, 350, and 500°C and the composition and properties of the thermolysis products are considered.
The oxidative thermolysis of the complexes yields mixtures of cobalt and copper oxides, including mixed ones. The reductive
thermolysis of the complexes yields a Co + Cu bimetallic powder in the case of compound I and a Co + Cu + C powder in the
case of compound II. The thermal behavior of the complexes is governed by the nature of the ligand coordinated to the copper
atom. The observed data are explicable in terms of the properties of this ligand. The chemistry of the oxidative and reductive
thermolysis is discussed.
Original Russian Text ? D.P. Domonov, S.I. Pechenyuk, N.L. Mikhailova, A.T. Belyaevskii, 2007, published in Zhurnal Neorganicheskoi
Khimii, 2007, Vol. 52, No. 7, pp. 1104–1110. 相似文献
4.
Ke-Wei Lei Hai-Mei Feng Jun-Long Wen Tian-Pin Shu 《Monatshefte für Chemie / Chemical Monthly》2010,33(3):743-747
Abstract
The 18-metallacrown-6 metallamacrocycle [Fe6(pmshz)6(C4H9NO)6] has been synthesized by the self-assembly reaction of iron ions with N-substituted salicylhydrazide ligands. Six Fe(III) ions and six deprotonated N-propanoyl-4-methylsalicylhydrazide (H3 pmshz) ligands construct a planar 18-membered ring based on Fe–N–N–Fe linkage. Because of the coordination, the ligand enforces the stereochemistry of the Fe(III) ions as a propeller shape with alternating …ΔΛΔΛ… configurations. There is a strong antiferromagnetic exchange interaction between the paramagnetic iron centers. 相似文献5.
Jae J. Koh Wook-Hwan Lee Paul G. Williard William M. Risen 《Journal of organometallic chemistry》1985,284(3):409-419
Hydrocarbon solutions of PtPCy3(C2H4)2 (Cy = cyclohexyl) react rapidly with 8-quinolinecarboxaldehyde (1 equiv.) to yield tricyclohexylphosphine quinolinecarboxyl platinum hydride (1) and CH2CH2 (2 equiv.). Compound 1 reacts with CCl4 in hydrocarbons to give PtPCy3(NC9H6CO)Cl (2) and CHCl3. The compound PtPCy3(C2H4)2 also reacts with Ph2P(C6H4-o-CHO) and Ph2As(C6H4-o-CHO) to give PCy3PtPh2P(C6H4-o-CO)(H) (3) and PCy3PtPh2As(C6H4-o-CO)(H) (4), respectively. Compounds 1, 2, 3, and 4 were characterized by infrared and 1H NMR spectra, and the crystal structure of 3 was determined by X-ray diffraction. Crystals of 3 are monoclinic, with space group P21/n and Z = 4 with the unit cell dimensions a 9.7936(17), b 14.844(35), c 23.530(64) Å, β 91.817 (18)°, and V 3419.09(1.36) Å3. The structure is refined to final discrepancy factors of R = 0.055, and Rw = 0.064. The molecular structure of 3 is that ligating atoms are in a plane containing Pt. The position of the hydride was not located crystallographically, but the 1H NMR spectrum of 3, supports the presence of a terminal hydride that is cis to the carbonyl. The IR band of 3 at 2023 cm?1 which is assigned to ν(PtH), and the hydride cleavage reaction of 1 with CCl4, provide evidence for the PtH bond. 相似文献
6.
Ray-Kuang Chiang Niang-Tsu ChuangChing-Shuei Wur Mong-Fu ChongChung-Rong Lin 《Journal of solid state chemistry》2002,166(1):158-163
A new hybrid organic-inorganic three-dimensional compound, [Co4(OH)2(H2O)2](C4H11N2)2[C6H2(CO2)4]2·3H2O 1, has been synthesized via hydrothermal reactions and characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and magnetic techniques. Compound 1 crystallizes in the monoclinic space group P21/n (no. 14) with a=6.3029(9) Å, b=16.413(2) Å, c=17.139(2) Å, β=98.630(2)°, V=1735.0(4) Å3, Z=2. Compound 1 contains tetranuclear Co4(μ3-OH)2(H2O)2 clusters that are inter-linked by pyromellitate bridging ligands into a three-dimensional structure containing one-dimensional tunnels along the a-axis with water and pendant monoprotonated piperazine molecules in the center. The variable temperature magnetic susceptibility was measured from 2 to 300 K at 5000 Oe showing a predominantly anti-ferromagnetic interaction in 1, and the field dependence of magnetization was measured at 2, 5, 15, and 20 K indicating the competition of magnetic interactions in the tetranuclear centers. 相似文献
7.
The interaction of [(η5-C5H4But)2YbCl · LiCl] with one equivalent of Li[(CH2) (CH2)PPh2] in tetrahydrofuran gave [Ph2PMe2][(η5-C5H4But)2Li] (1) and [(η5-C5H4But)2Yb(Cl)CH2P(Me)Ph2] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph2PMe2][CF3SO3] with two equivalents of (C5H4But)Li. Both compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. The solid state structure of 1 reveals a sandwich structure for the [(η5-C5H4But)2Li]− anion. 相似文献
8.
O. A. Efremova Yu. V. Mironov N. V. Kuratieva K.-K. Wang V. E. Fedorov 《Journal of Structural Chemistry》2010,51(4):782-784
Crystals of the rhenium cluster complex (H3O)4[(C2H5)4N]6[Th2Cl4(H2O)12O]3[Re4Se4(CN)12]4 are obtained in an acidic (HCl) aqueous solution by the reaction of cluster salt K4[Re4Se4(CN)12]·6H2O with ThCl4 and (C2H5)4NCl. Single crystal X-ray analysis shows that the title compound is ionic and crystallizes in the cubic crystal system (a = 22.7322(3) ?, V = 11746.93(27) ?3, Z = 2, I4 3m space group, R = 0.0350). It contains [Th2Cl4(H2O)12O]2+ cations with two thorium atoms bonded to each other through the bridging oxygen atom forming an angle of 180° in the structure. 相似文献
9.
George R. Clark Brian W. Skelton T.Nell Waters 《Journal of organometallic chemistry》1975,85(3):375-394
The crystal structure of tetrakis(methyldiphenylphosphine)iridium(I) tetrafluoroborate with cyclohexane of solvation, [Ir(PPh2Me)4]BF4·C6H12, has been determined from a three-dimensional X-ray analysis. The compound has been analysed in space group C2/c of the monoclinic system. There are twelve molecules (i.e. 1.5 molecules per asymmetric unit) in a cell of dimensions a = 36.804(8), b = 22.93(2), c = 21.676(4) Å, β = 121.41(1)°. Block-diagonal least-squares refinement has given a final R-factor of 0.060 for 7905 reflections having I > 3σ(I).The structure consists of two crystallographically distinct, but structurally similar molecules, one on a general position and one on a crystallographic two-fold axis. The phosphine ligands around the iridium atoms are in a very distorted square-planar arrangement. The reactions of the cation axe discussed in terms of this structure. 相似文献
10.
Diphenylcyclopropenethione reacts with Fe2(CO)9 in THF to give tetracarbonyl(diphenylcyclopropenethione)iron (C3Ph2S)Fe(CO)4. The crystal structure was determined by single crystal X-ray analysis. The compound crystallizes in the triclinic space group P with lattice constants a 1520.3(5), b 1026.1(3), c 933.5(2) pm; α 120.58(2), β 109.36(2), γ 111.72(2)°; Z 2. The molecule consists of an unchanged diphenylcyclopropenethione ligand coordinated via the sulphur atom to an Fe(CO)4 group in the axial position. The CS distance is 165.2(7) pm with an FeSC angle of 111.2(2)°. 相似文献
11.
《Journal of organometallic chemistry》2002,650(1-2):84-90
Reaction of YbI2 with two equivalents of cyclopentylindenyl lithium (C5H9C9H6Li) affords ytterbium(II) substituted indenyl complex (C5H9C9H6)2Yb(THF)2 (1) which shows high activity to ring-opening polymerization (ROP) of lactones. The reaction between YbI2 and cyclopentylcyclopentadienyl sodium (C5H9C5H4Na) gives complex [(C5H9C5H4)2Yb(THF)]2O2 (2) in the presence of a trace amount of O2, the molecular structure of which comprises two (C5H9C5H4)2Yb(THF) bridged by an asymmetric O2 unit. The O2 unit and ytterbium atoms define a plane that contains a Ci symmetry center. 相似文献
12.
The complex (di-η5-C5H4CH2CH2CH2C5H4)Ti(η1-C5H5)2 (I) can be obtained unambiguously starting from the corresponding bridged titanocene dichloride. Attempts to synthesize the isomeric compounds (η5-C5H5)2 Ti(di-η1-C5H4-CH2CH2CH2C5H4) (I′) by the action of a convenient bridged dianion on (C5H5)2 TiCl2 afford several compounds, one of them is the complex I. The possibility of interconversion of these complexes by a fluctional process is discussed. 相似文献
13.
14.
When excesses of ammonium thiocyanate and tetrabutylammonium chloride are added to an iron(III) solution, a water-insoluble ion-pair is formed. This compound is soluble in chloroform and other organic solvents. The variables affecting extraction with CHCl3 are studied in order to obtain the optimal conditions and an extraction procedure is proposed. The separation of iron as a previous step to its spectrophotometric determination is studied. 相似文献
15.
The tridentate chelate ligand bis(diphenylphosphinopropyl) amine and its title complex were prepared and characterized by31P n.m.r. and other spectroscopic data. Its activation energy EA for hydrogenation of cyclohexene is 52.3 kJ mol–1.
31P. 52,3 /.相似文献
16.
17.
The interaction of [(η5-C5H4But)2YbCl · LiCl] with one equivalent of Li[(CH2) (CH2)PPh2] in tetrahydrofuran gave [Ph2PMe2][(η5-C5H4But)2Li] (1) and [(η5-C5H4But)2Yb(Cl)CH2P(Me)Ph2] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph2PMe2][CF3SO3] with two equivalents of (C5H4But)Li. Both compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. The solid state structure of 1 reveals a sandwich structure for the [(η5-C5H4But)2Li]− anion. 相似文献
18.
The crystal and molecular structure of hexaphenylditin selenide (C6H5)3SnSeSn(G6H5)3 was determined by X-ray diffraction data and was refined to R 0.055. The compound is monoclinic, space group P21, with a 9.950(4), b 18.650(7), c 18.066(6) Å, β 106.81(4)°, Z 4. The two molecules in the asymmetric unit differ slightly in their conformations, both having approximate C2 symmetry. Bond lengths and angles are: SnSe 2.526 (2.521(3) ? 2.538(3)) Å; SnC 2.138 (2.107(16)?2.168(19)) Å; SnSeSn 103.4(1)°, 105.2(1)°. There are only slight angular distortions at the SnSeC3 tetrahedra (SeSnC angles: 104.3(5)?114.8(4)°). The bond data indicate essentially single bonds around the Sn atoms. 相似文献
19.
Three-coordinate RhX(PCy3)2 complexes (X = F, Cl, Br, I; Cy = cyclohexyl) have been prepared from rhodium(I) cyclooctene compounds. RhCl(PCy3)2 is in equilibrium with its dimer. The complexes RhX(PCy3)2 (X = Cl, Br, I) form the adducts RhX(PCy3)2(N2) with dinitrogen, the times for N2-fixation being 4 days, 3 hours and 15 minutes respectively. The three-coordinate complexes form four-coordinate dioxygen adducts RhX(PCy3)2(O2) which have unusually high ν(OO) at about 990 cm?1. This high frequency is attributed to the four-coordination, which is exceptional for dioxygen complexes. From RhF(PCy3)2 carbonyl, ethene, and diphenylacetylene complexes RhX(PCy3)2L (X = F, Cl, Br, I, N3, NCO, NCS; L = CO, C2H4, C2Ph2) (X = CN, NO3, acetate; L = CO) have been prepared. The trans-influence of the anionic ligands on the infrared frequencies of the neutral ligands is discussed in terms of the different π-bonding properties of the X- and L-ligands. 相似文献
20.