共查询到20条相似文献,搜索用时 15 毫秒
1.
Magdalena Jankowska Natalia Bespalova Bogdan Marciniec 《Journal of organometallic chemistry》2005,690(20):4492-4497
Cross-coupling of vinyldisilacyclobutane with a variety of olefins in the presence of [RuH(Cl)(CO)(PCy3)2] leads to stereoselective formation of functionalized vinyldisilacyclobutanes. Analogous homo-coupling of vinyldisilacyclobutane leads to the formation of E- and gem-bis(silyl)ethenes. The reaction offers a new route for synthesis of attractive monomers for ring opening polymerization (ROP). 相似文献
2.
Reaction of trans-[Pt(H)2(PCy3)2], 1, with [60]fullerene at room temperature affords [Pt(PCy3)2(η2-C60)], 2, in nearly quantitative yield. The most probable reaction pattern is the insertion of a fullerene 6,6 junction onto a Pt-H bond yielding an η1 alkyl derivative which, after hydrogen extrusion, gives 2. On the other hand, addition of 1 to different electron-deficient olefins, such as dimethyl maleate and fumarate, furnishes mixtures of both η1 metal—alkyl and η2 metal—olefin derivatives. If tetrachloroethylene is used as 2π component, trans-[PtCl(H)(PCy3)2] forms exclusively. 相似文献
3.
The crystal structure of [Ir(Me3TFB)(C6Me6)]ClO4 has been determined by X-ray diffraction. Lattice constants are a 16.9092(7), b 17.7120(7), c 16.8635(6) Å and β 97.984(3)° in a C2/c monoclinic lattice. The agreement factors are R, 0.038 and Rw 0.048 for the 3321 reflexions with I > 3σ(I). The coordination characteristics are similar to those of the corresponding rhodium analogues. 相似文献
4.
Hou DR Reibenspies J Colacot TJ Burgess K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(24):5391-5400
Phosphine oxazoline ligands la-j were converted to the corresponding [Ir(cod)(phosphine oxazoline)]+ complexes 2a-j. X-ray diffraction analyses of complexes 2b, 2h, 2i, and 2j were performed. The tert-butyl-, 1,1-diphenylethyl-, and phenyl-oxazoline complexes (2b, 2h, and 2i, respectively) had typical square planar metal environments with chair-like metallocyclic rings. However, the 3,5-di-tert-butylphenyl oxazoline complex 2j was distorted toward a tetrahedral metal geometry. This library of complexes was tested in asymmetric hydrogenations of several arylalkenes. High enantioselectivities and conversions were observed for some substrates. A possible special role for the HPh2C-oxazoline substituent in asymmetric hydrogenations was identified and is discussed. In attempts to rationalize why high enantioselectivities were not observed for some alkenes, a series of deuterium labeling experiments were performed to probe for competing reactions that occurred prior to the hydrogenation step. Double bond migrations were inferred for several substrates, and this is a significant complication in asymmetric hydrogenations of arylalkenes that had not been discussed prior to this study. A mechanistic rationale is proposed involving competing double bond migration for some but not all substrates. Appreciation of this complication will be valuable in further studies aimed at optimization of enantioselection in asymmetric hydrogenations of unfunctionalized alkenes. 相似文献
5.
M. Valderrama M. Scotti R. Ganz L.A. Oro F.J. Lahoz C. Foces-Foces F.H. Cano 《Journal of organometallic chemistry》1985,288(1):97-107
The preparation of cationic arenerhodiiim(I) complexes of the type [Rh(DQ)-(arene)]PF6 (DQ = duroquinone; arene = C6H6-nMen, n duroquinone complexes with Group VB donor ligands are described. The crystal structure of [Rh(DQ)(C6H5Me)]PF6 has been determined by X-ray diffraction. The compound crystallizes in the P21/n space group, in a unit cell of dimensions a 15.9866(5), b 11.8438(3), c 9.9968(3) Å, β 98.473(4)Å. The structure was solved by Patterson and Fourier methods and refined to R and Rw values of 0.062 and 0.076, respectively. The Rh atom is coordinated to a toluene group (η6) and a duroquinone ligand (η4), which eclipse each other. Both ligands are distorted to adopt boat-like conformations. 相似文献
6.
7.
James A. Kaduk Arthur T. Poulos James A. Ibers 《Journal of organometallic chemistry》1977,127(2):245-260
The structure of (η3-allyl)carbonylchlorobis(dimethylphenylphosphine)-iridium(III) hexafluorophosphate, [Ir(η3-C3H5)Cl(CO)(P(CH3)2(C6H5))2][PF6], has been determined from three-dimensional X-ray data to add support for a proposed mechanism of the oxidative addition of allyl halides to IrX(CO)(PR3)2 (X = halide). The compound crystallizes in space group C52h-P21/c with four formula units in a cell of dimensions a = 11.027(1), b = 12.230(2), c = 19.447(5) Å, and β = 103.16(2)0. Least-squares refinement of the structure has led to a value of the conventional R index (on F) of 0.066 for the 3018 independent reflections having F20>3—(F20). The crystal structure consists of discrete, monomericions. The hexafluorophosphate anion is disordered. The coordination geometry around the iridium atom may be described as octahedral, with the chloro ligand trans to the carbonyl group and each phosphorus atom trans to a terminal carbon of the allyl group. Structural parameters: Ir—P = 2.366(4), 2.347(3);Ir—Cl = 2.389(3); Ir—C(allyl) = 2.28(1), 2.24(1),2.25(1); Ir—C (carbonyl) = 1.85(1) Å; P—Ir—P = 105.7(1); C(terminal)—Ir—C(terminal) = 66.2(8); C—C—C = 125(2)o. The allyl group makes an angle of 126o with the P—Ir—P plane. Correlations between geometric structure and number of d electrons are noted among several M—C3H5-complexes, and are interpreted in the light of theoretical models of the M—C3H5- bond. 相似文献
8.
A new ruthenium hydride species, showing high catalytic isomerization and hydrogenation properties, was isolated via a ligand exchange reaction. The same species was also present in the mixture of degradation products of the monophosphinic complex RuCl(CO)(PCy)3(IPr)CH(Ph), 3, after reaction with alcohols under basic conditions. 相似文献
9.
Massimo Di Vaira Fabrizio Mani Piero Stoppioni 《Journal of organometallic chemistry》2004,689(10):1757-1762
The reaction of [CpRu(CH3CN)3]PF6 with the bidentate ligands L-L=1,2-bis(diphenylphosphino)ethane, dppe, and (1-diphenylarsino-2-diphenylphosphino)ethane, dpadppe, affords mononuclear or dinuclear complexes of formula [CpRu(η2-L-L)(CH3CN)]PF6, [{CpRu(CH3CN)2}2(μ-η1:1-L-L)](PF6)2 and [{CpRu(CH3CN)}2(μ-η1:1-L-L)2](PF6)2 (L-L=dppe, dpadppe). All of the compounds are characterized by microanalysis and NMR [1H and 31P{1H}] spectroscopy. The crystal structure of [{CpRu(CH3CN)2}2(μ-η1:1-dppe)](PF6)2 has been determined by X-ray diffraction analysis. The complex exhibits a dppe ligand bridging two CpRu(CH3CN)2 fragments. 相似文献
10.
R. Usón L.A. Oro D. Carmona M.A. Esteruelas C. Foces-Foces F.H. Cano S. García-Blanco A.Vázquez De Miguel 《Journal of organometallic chemistry》1984,273(1):111-128
A new series of cationic areneiridium(I) complexes of formula [Ir(barrelene)(arene)]+ or [Ir(barrelene)(PhNRPh)]+ (R= Ph or H) have been synthesized from neutral iridium complexes of the type [IrY(barrelene)]x (barrelene = Me3TFB, Y = Cl or OMe (x = 2), Y = acac (x = 1); barrelene = TFB, Y = OMe (x = 2), Y = acac (x = 1)). The crystal structures of [Ir(Me3TFB)(1,4-C6H4Me2)]ClO4 and [Ir(TFB)(PhNPh2)]BF4·CH2Cl2 have been determined by X-ray diffraction. They crystallize in the space groups Pbca and Pna21 respectively with lattice constants of 17.6947(11), 15.8072(10), 16.0019(11) Å and 9.8059(2), 20.8097(9), 14.3367(4) Å. Final R factors were 0.063 and 0.042 for the observed data. Both complexes show a staggered arrangement between the arene and the TFB moieties and deviation from planarity of the coordinated arene ligands. In the second complex the IrC and NC distances, the CNC angle, the type of arene puckering, and the spectroscopic data indicate a distortion of the coordinated arene towards a η5-coordinated iminocyclohexadienyl form. 相似文献
11.
Treatment of several cyclic olefins and allybenzene with a catalytic amount of [Rh3O(OAc)6(H2O)3]OAc in acetic acid in the presence of t-butyl hydroperoxide affords the corresponding α,β-unsaturated carbonyl compounds (enones) highly seletively via an ionic pathway. 相似文献
12.
Matthew HesfordWilliam Levason Simon D. OrchardGillian Reid 《Journal of organometallic chemistry》2002,649(2):214-218
The syntheses and spectroscopic characterisation of the new facultative tridentate tellurium containing ligands MeS(CH2)3Te(CH2)3SMe (S2Te) and H2N(CH2)3Te(CH2)3NH2 are described. The complexes of the former, fac-[Mn(CO)3(S2Te)]CF3SO3, [Rh(Cp*)(S2Te)][PF6]2, [MCl(S2Te)]PF6 (M=Pd or Pt), [Cu(S2Te)]BF4 and [Ag(S2Te)]CF3SO3 have been prepared and characterised by analysis, IR, 1H-, 13C{1H}-, 125Te- and 195Pt-NMR spectroscopy and mass spectrometry. The X-ray crystal structures of [Rh(Cp*)(S2Te)][PF6]2 and [PtCl(S2Te)]PF6 are described. The results are compared with those obtained from complexes of the related tridentates Te{(CH2)3TeR}2, Se{(CH2)3SeMe}2 and S{(CH2)3SR}2. 相似文献
13.
14.
Thermal displacement of coordinated nitriles RCN (R = CH3, C2H5 or n-C3H7) in [C5H5Fe(L2)(NCR)]X complexes (L2 = P(OCH3)3)2, (P(OC6H5)3)2 or (C6H5)2PC2H4P(C6H5)2 (DPPE)) by E(CH3)2 affords high yields of [C5H5Fe(L2)(E(CH3)2)]X compounds (E = S, Se and Te; X = BF4 or PF6). Spectroscopic data and ligand displacement reactions are presented and discussed together with related observations on [C5H5Fe(CO)2(E(CH3)2)]BF4 compounds. The molecular structure of [C5H5Fe(P(OCH3)3)2(S(CH3)2)]PF6 was determined by a single-crystal X-ray diffraction study: monoclinic, space group P21/n-C52h (No. 14) with a = 8.4064(12), b = 11.183(2), c = 50.726(8) Å, β = 90.672(13)° and Z = 8 molecules per unit cell. The coordination sphere of the iron atom is pseudo-tetrahedral with an Fe---S bond distance of 2.238 Å. 相似文献
15.
D.E. Games L.A.P. Kane-Maguire D.A. Sweigart 《Journal of organometallic chemistry》1982,234(3):323-327
Field desorption mass spectra are reported for a range of [M(CO)3(η-arene)]X (MMn or Re, XBF4 or PF6) salts. In most cases the spectra are simple, being dominated by molecular, [M]+·, [M + 1]+, and [MCO]+ ions for the cationic part of their structure. However, with the π-chloroarene complexes [Mn(CO)3(η-ClC6H5)]PF6 and [Mn(CO)3(η-1-Cl, 4-MeC6H4)]PF6, facile loss of the chloro substituent and further fragmentation leads to unusually complex spectra, which include strong peaks arising from recombination of fragment species. Cluster ions are also noted in several cases, allowing identification of the anion. 相似文献
16.
The [ReOBr3(dppe)] (dppe=bis(diphenylophosphino)ethane) complex reacts with acetonitrile in the presence of excess of triphenylphpsphine to give a new monomeric nitrile rhenium(III) complex—[ReBr3(MeCN)(dppe)] (1). The reaction of 1 with gaseous nitric oxide leads to the mixed [ReBr3(NO)(dppe)]0.57[ReOBr3(dppe)]0.43 complex (2) with rhenium atoms on +2 and +5 oxidation states. This paper presents the synthesis, spectroscopic characterisation and X-ray structure of 1 and 2. The geometries of [ReBr3(NO)(dppe)] and [ReOBr3(dppe)] have been optimized using the density functional theory (DFT) and the electronic transitions of [ReBr3(NO)(dppe)] and [ReOBr3(dppe)] have been calculated with the time-dependent DFT method (TDDFT). The UV–vis spectrum of 2 has been interpreted on the basis of the experimental data for [ReOBr3(dppe)] and the calculated transitions for [ReOBr3(dppe)] and [Re(NO)Br3(dppe)]. 相似文献
17.
Caifang Han E. Zhang Xiangqing Feng Shoufeng Wang Haifeng Du 《Tetrahedron letters》2018,59(14):1400-1403
A metal-free hydrogenation of 2-quinolinecarboxylates has been realized by using 5?mol% of B(C6F5)3 as catalyst. A variety of tetrahydroquinolines were obtained in 57–99% yields. An attempt for the asymmetric hydrogenation with chiral boron Lewis acids generated from chiral dienes afforded very low ee’s. 相似文献
18.
S. I. Pechenyuk D. P. Domonov D. L. Rogachev A. T. Belyavskii 《Russian Journal of Inorganic Chemistry》2007,52(7):1033-1038
The thermolysis of complexes [Co(NH3)6][Fe(CN)6] and [Co(NH3
6]4[Fe(CN)6]3 under an air or hydrogen atmosphere at 200, 350, and 500°C is studied. The composition and properties of thermolysis products
are determined. The oxidative thermolysis yields mixtures of oxides of the central metals; the reductive thermolysis yields
intermetallic compounds CoFe. The density of the complexes and the specific surface area of the intermetallic compounds are
measured. Average particle sizes are calculated. The morphology and dispersion of the powders are dictated by the shape and
density of the crystals of the precursor double salts and the thermolysis temperature. The thermolysis chemism in the oxidative
and reductive atmospheres is discussed in the context of the nature of the complex anion.
Original Russian Text ? S.I. Pechenyuk, D.P. Domonov, D.L. Rogachev, A.T. Belyavskii, 2007, published in Zhurnal Neorganicheskoi
Khimii, 2007, Vol. 52, No. 7, pp. 1110–1115. 相似文献
19.
Richard D. Adams Fang Fang Mark D. Smith Qiang Zhang 《Journal of organometallic chemistry》2011,696(17):2904-2909
A reinvestigation of the reaction of Ir(CO)Cl(PPh3)2, 1 with HSnPh3 has revealed that the oxidative-addition product Ir(CO)Cl(PPh3)2(H)(SnPh3), 2 has the H and SnPh3 ligands in cis-related coordination sites. Compound 2 reacts with a second equivalent of HSnPh3 by a Cl for H ligand exchange to yield the new compound H2Ir(CO)(SnPh3)(PPh3)2, 3. Compound 3 contains two cis- related hydride ligands. Under an atmosphere of CO, 1 reacts with HSnPh3 to replace the Cl ligand with SnPh3 and one of the PPh3 ligands with a CO ligand and also adds a second equivalent of CO to yield the 5-coordinate complex Ir(CO)3(SnPh3)(PPh3), 4. Compound 4 reacts with HSnPh3 by loss of CO and oxidative addition of the Sn-H bond to yield the 6-coordinate complex HIr(CO)2(SnPh3)2(PPh3), 5 that contains two trans-positioned SnPh3 ligands. 相似文献
20.
Coordination polymers [Ag(Me4Pyz)] PF6(I) and [Ag2(Me4Pyz)3](BF4)2·H2O (II) have been synthesized, and their structures have been determined. The crystals of I are monoclinic, space group C2/c, a = 9.440(2) ?, b = 10.587(2) ?, c = 13.165(3) ?, β= 107.19(3)°, V = 1257.0(5) ?3, d = 2.056 g/cm3, Z = 4. The crystals of II are monoclinic, space group P21/n, a = 13.062(3) ?, b = 12.259(2) ?, c = 18.996(4) ?, β = 97.73(3)°, V = 3014.1(11)?3, ρ = 1.798 g/cm3, Z = 4. The structure of I is built of linear polymeric cations [Ag(C8H12N2)]
∞
+
and octahedral anions [PF6]−. Upon the interaction of tetramethylpyrazine molecule with Ag+ ions, intersecting polymeric chains [Ag(C8H12)]
∞
+
(1D polymer) are formed extending in mutually perpendicular diagonal directions. The structure of II consists of layers (2D polymers) formed by fused sixmembered rings. These rings consist of Ag+ ions linked by bridging ligands Me4Pyz.
Original Russian Text ? Yu.V. Kokunov, Yu.E. Gorbunova, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52,
No. 5, pp. 743–750. 相似文献