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101.
102.
103.
New mixed-ligand copper(I) complexes, [Cu(Phca2en)(PPh3)X], [Phca2en = N,N′-bis(β-phenylci-nnamaldehyde)-1,2-diiminoethane and X=Cl (1), Br (2), I (3), NCS (4), N3 (5)] have been synthesized and characterized by various techniques. 1H and 13C-NMR and IR spectral data of these copper(I) complexes are compared with the free ligand to elucidate some structural features. The structures of [Cu(Phca2en)(PPh3)Br] (2) and [Cu(Phca2en)(PPh3)I] (3) have been determined from single-crystal data showing that the coordination geometry around copper atom is a distorted tetrahedron. Furthermore, these Cu(I) complexes exhibit supramolecular motifs of the type multiple phenyl embraces resulting from attractive interactions between phenyl rings of PPh3 moieties. The presence of the C–H…Cu weak intramolecular hydrogen bonds, due to the trapping of C–H bonds in the vicinity of the metal atoms, is also reported. 相似文献
104.
Daniel L. Reger Russell P. Watson Mark D. Smith 《Journal of organometallic chemistry》2007,692(24):5414-5420
The new heterometallic complex {μ-1,3,5-[CH(pz)2]3C6H3}[Re(CO)3Br][Pt(p-tolyl)2]2 has been prepared by reaction of 1 equiv. of the dimer [Pt(p-tolyl)2(μ-SEt2)]2 with the monometallic rhenium precursor {1,3,5-[CH(pz)2]3C6H3}Re(CO)3Br, where 1,3,5-[CH(pz)2]3C6H3 is the tritopic, arene-linked bis(pyrazolyl)methane ligand 1,3,5-tris[bis(1-pyrazolyl)methyl]benzene. Similarly, the heterometallic complex {μ-1,3,5-[CH(pz)2]3C6H3}[Re(CO)3Br]2[Pt(p-tolyl)2] has been made by the reaction of the dirhenium compound {μ-1,3,5-[CH(pz)2]3C6H3}[Re(CO)3Br]2 and one-half of an equivalent of [Pt(p-tolyl)2(μ-SEt2)]2. X-ray crystallographic studies of the new compounds reveal significant noncovalent interactions in their molecular and supramolecular structures. 相似文献
105.
ShiGuoSUN XiaoJunPENG MingWenFAN YongQianXU LeiSHI LiChengSU 《中国化学快报》2004,15(8):965-968
Two novel rhenium(I) 2, 2′-bipyridyl complexes, [(4,4′-di-COOEt-bipy) Re(CO)3 (NCCH3)PF6] and [(4,4′-di-COOEt-bipy) Re (CO)3 (NCS)], a model complex [(4,4′-di-COOEt-bipy) Re (CO)3 (pyridine)PF6], were synthesized. Their ground state electronic spectra and emission spectra were measured in acetonitrile. The MLCT absorption maximum of the complex exhibited a considerable red shift as the ligand changed from pyridine to CNCH3, or SCN. 相似文献
106.
Franz Pertlik 《Monatshefte für Chemie / Chemical Monthly》1988,119(4):451-456
The crystal structures of five isotypic hexagonal compounds with general formulaMAs4O6
X [M=K, NH4;X=Cl, Br, I; space group: P622;Z=1] were determined from 370 single crystal X-ray data and refined toR values <0.05. The structure type is characterized by neutral charged
[As2O3] sheets arranged parallel (00.1). The As atoms of neighbouring two sheets point to each other and the sheets are combined by interlayeredM andX atoms, respectively. TheM atoms are coordinated to twelve oxygen atoms, theX atoms are coordinated to twelve arsenic atoms. In both cases the coordination polyhedron is a hexagonal prism. The compounds were synthesized by thermal treatments of cubic As2O3 and potassium or ammonium haloids in a saturated aqueous solution of potassium acetate resp. ammonia [500 K, saturation vapour pressure].
Die Verbindungen KAs4O6 X (X=Cl, Br, I) und NH4As4O6 X (X=Br, I): Hydrothermalsynthese und Strukturbestimmung
Zusammenfassung Die Kristallstrukturen der fünf isotypen hexagonalen Verbindungen mit der allgemeinen FormelMAs4O6 X [M=K, NH4;X=Cl, Br, I; Raumgruppe: P622;Z=1] wurden anhand von 370 Einkristall-Röntgendaten bestimmt und aufR-Werte <0.05 verfeinert. Der Strukturtyp ist ausgezeichnet durch neutrale [As2O3]-Schichten, die parallel (00.1) angeordnet sind. Die As-Atome zweier benachbarter Schichten weisen jeweils aufeinander zu, und die Schichten selbst werden durch zwischengelagerteM- bzw.X-Atome verbunden. DieM-Atome werden jeweils von zwölf O-Atomen, dieX-Atome von zwölf As-Atomen umgeben. Das Koordinationspolyeder ist in beiden Fällen ein hexagonales Primsa. Die einzelnen Verbindungen wurden unter Hydrothermalbedingungen aus kubischem As2O3 und dem jeweiligen Kalium- oder Ammoniumhalogenid in einer gesättigten wäßrigen Lösung von Kaliumacetat bzw. Ammoniak synthetisiert (500 K, Sättigungsdampfdruck).相似文献
107.
The reaction between thallium(I) and [CoIIIW12O40]5- in the presence of ruthenium(III) as catalyst proceeds viainitial outer-sphere oxidation of the catalyst to ruthenium(VI). The ruthenium(IV) thus generated will oxidize thallium(I)
to an unstable thallium(II) which by reacting with oxidant gives the final product, thallium(III). The formation of ruthenium(II)
by direct two-electron reduction of the catalyst by thallium(I) is thermodynamically less favorable. The reaction rate is
unaffected by the [ H+ ], whereas it is catalyzed by chloride ion . The formation of reactive chlorocomplex,TlCl, in a prior equilibrium is the
reason for the chloride ion catalysis. Increasing the relative permittivity of the medium increases the rate of the reaction,
which is attributed to the formation of an outer-sphere complex between the catalyst and oxidant.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
108.
Sabry A. El-Korashy 《Monatshefte für Chemie / Chemical Monthly》2002,133(3):333-343
Summary. Solid crystalline calcium silicate hydrate (I) synthesized from equimolar amounts of Ca and Si under hydrothermal conditions
at 120°C shows cation exchange properties towards divalent metal cations such as Ni, Cu, Cd, or Hg. It also exhibits caesium
selectivity in the presence of Na+. The exchange capacity and selectivity of the solid can be increased by 10 and 28%, respectively, upon substitution of 0.01 mol
of the Ca2+ in its structure by Na+. The ability of metal cation uptake by the solid was found to obey the order Ni2+ > Hg2+ > Cu2+ > Cd2+. The different affinities of calcium silicate hydrate (I) towards these ions can be used for their separation from solutions
and also in nuclear waste treatment. The mechanism of the exchange reaction is discussed.
Received June 11, 2001. Accepted September 10, 2001 相似文献
109.
Kai-Ming Chi Hung-Chang Houa Kuo-Hsien Chen Shin-Guang Shyu Yuh-Sheng Wen 《中国化学会会志》1995,42(3):547-554
Copper(I) complexes of general formula (β-diketonate)Cu(7-AcO-NBD), where 7-AcO-NBD = 7-norbornadienyl acetate and β-diketonate = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate (1), 1,1,1-trifluoro-2,4-pentanedionate (2), 2,4-pentanedionate (3), 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate (4), 4,4,4-trifluoro-1-phenyl-1,3-butanedionate (5), were prepared from reactions of CuCl with Na(β-diketonate) in the presence of 7-AcO-NBD. AH compounds were characterized by elemental analyses, 1H, 13C, 19F NMR and IR spectra. Single-crystal strucutre of compound 1 was determined by X-ray diffraction analysis that showed a mononuclear copper species with coordination of a chelating β-diketonate ligand through two oxygen atoms and the 7-AcO-NBD through its C? C double bond and an oxygen atom in the solid state. For compound 1, the crystal data are: triclinic, space group $ {\rm P}\bar 1 $, a= 5.4519(14) Å, b= 11.852(3) Å, c= 13.304(3) Å, α = 74.721(20)° β = 80.220(20)°, γ= 76.848(19)°, Z = 2, RF = 0.060 and Rw = 0.064. Hot-wall chemical vapor deposition experiments revealed that compound 1 is suitable as a precursor for deposition of copper films in the temperature range 170–260 °C. 相似文献
110.
Alkyl substituted chromium Fischer carbene complexes react with 1,1-diphenylallene in the presence of rhodium(I) catalysts (10 mol%) to yield highly substituted dienyl indenone derivatives. In this process a catalytic chromium(0)-rhodium(I) exchange occurs, four new C-C bonds are created, and four-components (two allenes, the carbene ligand and one CO ligand) are joined in a chemo- and regioselective manner. 相似文献