共查询到20条相似文献,搜索用时 765 毫秒
1.
Melvyn Rowen Churchill Clifford Bueno David A. Young 《Journal of organometallic chemistry》1981,213(1):139-150
The species FeRu3(CO)13(μ-PPH2)2, synthesized from Ru3(CO)12 and Fe(CO)4(Ph2PPPh2),has been characterized both spectroscopically and via a single-crystal X-ray structural analysis. This complex crystallizes in the centrosymmetric triclinic space group P [No. 2, Ci1] with a 10.066(3), b 12.899(3), c 17.003(4) Å, α 111.89(2), β 91.02(2), γ 102.00(2)°, V 1992.7(9) Å3, Z 2, ?(obsd) 1.79(2) g cm-3 and ?(calcd) 1.82 cm-3. Diffraction data were collected with a Syntex P21 automated four-circle diffractometer and the structure was refined to RF 6.0% and RWF 3.6% for all 5213 reflections (RF 3.8%, RWF 3.6% for those 4140 reflections with |Fo|> 3σ(|Fo|).The metal atoms define a planar triangulated rhombus, with atoms Ru(1) and Ru(2) at the bridgehead, and Fe(1) and Ru(3) at the acute apices. Fe(1) is linked to four terminal carbonyl ligands and is associated with the heteronuclear bonds Fe(1)Ru(1) 2.861(1) Å and Fe(1)Ru(2) 2.868(1) Å. The ruthenium atoms are each bonded to three terminal carbonyl groups. The retheniumruthenium distances are Ru(1)Ru(2) 3.098(1), Ru(1)Ru(3) 3.147(1), and Ru(2)Ru(3) 3.171(1) Å. The structure is completed by Ph2P bridges across the Ru(1)Ru(3) and Ru(2)(ru(3) vectors (<Ru(1)P(1)Ru(3) 84.89(5)° and <Ru(2)P(2)Ru(3) 85.56(6)°). 相似文献
2.
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
3.
Aristides Christofides Judith A.K. Howard John L. Spencer F.Gordon A. Stone 《Journal of organometallic chemistry》1982,232(3):279-292
Bis(cycloocta-1,5-diene)platinum reacts with 2,3,4,5-tetraphenylfulvene to afford the complex [Pt(η2-CH2C5Ph4)(cod)] (cod C8H12) in which the metal atom is coordinated to the exo-cyclic double bond of the fulvene. Related compounds [Pt(η2-CH2C5Ph4L2] (L PPh3, PMePh2, PMe2Ph, AsPh3 or CNBut have also been prepared and characterised. Reaction of the complexes [Pt(C2H4)2(L)] (L P(cyclo-C6H11)3, PPh3 or AsPh3) with 2,3,4,5-tetraphenylfulvene yields the compounds [Pt(C2H4)(η2-CH2C5PH4)(L)]. NMR data for the new species are reported and discussed. 6,6-Diphenylfulvene reacts with [Pt(cod)2] and PPh3 ( mol ratio) to give the complex [Pt(η2-C5H4CPh2)-(PPh3)2] in which the metal atom is bonded to carbon atoms C(2) and C(3) of the fulvene ring. This was established by an X-ray diffraction study. Crystals are monoclinic, space group P21/n, with Z 4 in a unit cell of dimensions a 13.761(4), b 21.653(13), c 17.395(6) Å, β, 104.46(2)°. The structure has been solved and refined to R 0.064 (R′ 0.064) for 3139 independent diffracted intensifies measured at room temperature. The platinum atom is in a trigonal environment formed by the two ligated phosphorus atoms and the CC bond of the fulvene which is elongated to 1.52(3) Å. The c5 fulvene ring is planar, and makes an angle of 108° with the coordination plane around the platinum. In this plane the metal atom is slightly asymmetrically bonded with PtC 2.15(2) and 2.24(2) Å, and PtP 2.280(6) and 2.301(6) Å. 相似文献
4.
C. Anklin P.S. Pregosin F. Bachechi P. Mura L. Zambonelli 《Journal of organometallic chemistry》1981,222(1):175-185
Platinum(II) and palladium(II) complexes containing chelating acyl ligands have been synthesized from salicylaldehyde, 2-hydroxynaphthaldehyde and 2-hydroxy-3-methoxybenzaldehyde. The platinum(II) complexes [Pt(acyl)L2], acyl OC6H4CO, OC10H6CO, O(m-CH3OC6H3CO), L tertiary phosphine, 1/2 diphenylphosphinoethane, can be isolated with both monodentate and chelating diphosphines, whereas for palladium only the compounds with chelating phosphines are readily obtainable. The reactions of [Pt(OC6H4CO)L2] with HCl afford trans-[PtCl(OHC6H4CO)L2], L monodentate tertiary phosphine and cis-[PtCl(OHC6H4CO)L2], L2 1,2-bis-diphenylphosphinoethane, in which the metal—carbon bond remains intact. The structure of [Pt(OC6H4CO)-(P(p-CH3C6H4)3)2] has been determined by X-ray diffraction methods and found to have the expected square planar structure. Some relevant bond lengths and angles are: PtP; 2.271(4) and 2.348(5) Å; PtC; 1.96(2) Å and PtO; 2.07(1) Å; PPtP 101°, CPtO 82°. 相似文献
5.
《Journal of organometallic chemistry》1988,342(2):209-214
Crystals of [Mo(η5-C5H5)2(NH3)(SC6H5)][PF6] · (CH3)2CO solvate are monoclinic, space group P21/n, a 9.777(1), b 11.6343(2), c 19.656(4) Å, β 93.60(1)°, V 2231-46 Å3, Z Dc 1.617 g cm−3, μ(Mo-Kα) 7.21 cm−1. The structure was solved by Patterson and difference Fourier electron density synthesis and refined to R (F) 0.047 and Rw(F) 0.057 for 3293 observed reflections. The molybdenum atom has the usual distorted tetrahedral geometry comprising the two MoCp (Cp η5-C5H5) ring normals (MoCp 1.988(13), 1.989(15) Å), one Mo-NH3 (MoN 2.226(12) Å), and one MoSc6H5 (MoS 2.465(5) Å). Extended HMO and steric energy calculations were made in order to account for the geometry adopted by the thiolato ligand in this complex. 相似文献
6.
7.
8.
The reaction of Rh(CO)2acac with triphenylantimony in the presence of cesium benzoate in tetraethylene glycol/dimethyl ether solution resulted in the selective formation of [Rh12Sb(CO)27]3- (66% yield) after 3 h of contact time under ≈400 atm of carbon monixide and hydrogen (CO/H2 1) at 140–160°C. The cluster has been isolated as the [Cs(18-Crown-6)2]+, [(CH3)4]+, [(C2H5)4N]+, (Ph3P)2N]+ and [PhCH2N(C2H5)3]+ salts. The [(C2H5)4N]3 [Rh12Sb(CO)27] complex has been characterized via a complete three-dimensional X-ray diffraction study. The complex crystallizes in the space group Rc with a 23.258(13) Å, c 22.811(4) Å, V 10 686 Å3 and p(calcd.) 2.334 g cm-3 for mol.wt. 2503.66 and Z 6. Diffraction data were collected with an Enraf-Nonius CAD 4 automated diffractometer using graphite-monochromatized Mo-Kα radiation. The structure was solved by direct methods and refined by difference-Fourier and least-squares techniques. All non-hydrogen atoms have been located and refined: final discrepancy indices are Rf 3.5% and Rwf 4.6% for 3011 reflections. The anion's structure consists of twelve rhodium atoms situated at the corners of a distorted icosahedron with contacts of 2.807(1), 2.861(1), 2.874(1), 2.999(1), 3.017(1) and 3.334(1) Å and rhodium—antimony contacts of 2.712(0) Å. Rhodium—rhodium bond distances of 2.807 and 3.017 Å are in the range usually found for these complexes although a distance of 3.334 Å may be longer than expected from bonding interactions. The sum of the covalent radii of antimony and rhodium, 2.80 Å, is intermediate between the two observed RhSb contacts. The anion cluster structure is that of distorted icosahedron. This polyhedron has previously been found in [B12H12]2- but not with transition metal clusters. A comparison between the structures of rhodium carbonyl clusters and boranes shows the occurrence of similar structural features. Applications of bonding theories based on the boranes, such as Wade's rules, to rhodium carbonyl clusters shows the extent in which these rules are obeyed. 相似文献
9.
Edward J. Miller Arnold L. Rheingold Thomas B. Brill 《Journal of organometallic chemistry》1984,273(3):377-383
[η5-C5(CH3)5]Co(O2C6H4) crystallizes in the orthorhombic space group Pnma with a 12.942(4), b 12.902(4), c 8.543(3) Å, V 1426(1) Å3, and Z = 4. Least-squares refinement of 1688 independent observed reflections, F(obs) ? 2.5σ(Fobs), gives RF 3.79 and RwF 3.72%. The cyclopentadienyl ring contains two short (1.412(3) Å) and three longer (〈av〉 1.430(4) Å) CC bond lenghts, consistent with a slight preference for diolefin bonding. The O2C6H4 fragment is best described as a catecholate with a CO bond distance of 1.338(3), and a CoO distance of 1.837(2) Å. 相似文献
10.
G.R. Clark T.J. Collins K. Marsden W.R. Roper 《Journal of organometallic chemistry》1983,259(2):215-232
Reaction of HgR2 with OsHCl(CS)(PPh3)3 yields red, five-coordinate, OsRCl-(CS)(PPh3)2 (R = p-tolyl). From this have been derived the compounds OsRX(CS)(PPh3)2 with X = Br, I, S2CNEt2, O2CMe, O2CCF3. These compounds add an additional ligand, MeCN, CO or CNR to form colourless, six coordinate arylthiocarbonyl complexes, which undergo migratory-insertion reactions to form red, dihapto-thioacyl complexes. The crystal structure of a representative example, Os(η2-CSR)(η1-O2CCF3)(CO)PPh3)2 has been determined. The red equant crystals are orthorhombic, space group P212121, a 11.584(1), b 19.184(2), c 18.90(1) Å, V 4199 Å3, Z 4. The structure was solved by conventional heavy-atom methods and refined by full-matrix least-squares employing anisotropic thermal parameters for all non-hydrogen atoms except the carbon atoms of the triphenylphosphines. The final R factor is 0.057 for 2868 observed reflections.The coordination geometry in the monomeric complex is that of an octahedron distorted by the constraints of the ligands. The triphenyl phosphine ligands are mutually trans; the equatorial plane contains carbonyl, monohapto-trifluoroacetate, and dihapto-thioacyl ligands. Bond distances and angles are OsP 2.405, 2.407(4) Å; POsP 173.9(1)°; OsCO 1.83(2) Å; Os-O (trifluoroacetate) 2.206(11) Å; OsC (thioacyl) 1.91(2); OsS 2.513(6); CS 1.72 Å. The CS bond length implies a reduction in bond order from 2.0 to approx. 1.5 upon coordination to the metal.The η2-thioacyl ligand in Os(η2-CSR)Cl(CNR)(PPh3)2 is methylated with methyl triflate and further reaction with LiCl produces the thiocarbene complex OsCl2(C[SMe]R)(CNR)(PPh3)2. 相似文献
11.
Michael I. Bruce Trevor W. Hambley MichaeL R. Snow A.Geoffrey Swincer 《Journal of organometallic chemistry》1982,235(1):105-112
The title complex was obtained from the adduct of C2(CN)4 and Rh(CCPh)-(CO)(PPh3)2 by simple substitution of CO in refluxing acetonitrile. Crystals of the complex are orthorhombic, with a 10.058(2), b 20.008(4), c 21.594(5) Å, space group P212121, Z 4. The rhodium has approximate trigonal bipyramidal coordination, with apical NCMe and C2Ph ligands: RhC2Ph, 1.939(18); RhC(olefinic), 2.151, 2.157(19); RhN, 2.051(16); RhP, 2.377, 2.397(6) Å. 相似文献
12.
13.
The crystal and molecular structure of 3,4-quinoxalino-1-tellura(II)cyclopentane has been determined by X-ray diffraction at room temperature. The crystals are tetragonal, space group I41/a with a = b = 25.315(8), c = 6.010(1) Å and V = 3851.38 Å3. The density of 1.96 g cm?3 calculated on the basis of 16 molecules per unit cell is in agreement with the flotation value of 1.91 g cm?3. The structure has been refined to a conventional R value of 0.0408 using 744 independent observed reflections obtained from four-circle diffractometer measurements. The structure consists of discrete molecules TeC = 2.134 Å (av.), CN = 1.343 Å (av.) and angle CTeC = 80.7° (e.s.d. 0.5) but the intermolecular TeTe bonds (3.791 and 3.998 Å) are less than the sum of the Van der Waals' radii thus indicating the presence of secondary bonding. These short intermolecular contacts in the crystal structure are consistent with the anomalous physical properties observed. 相似文献
14.
Crystal and molecular structure of tricyclopentadienyltetrahydrofuranuranium(III), (η5-C5H5)3U·OC4H8
H.J. Wasserman A.J. Zozulin D.C. Moody R.R. Ryan K.V. Salazar 《Journal of organometallic chemistry》1983,254(3):305-311
Tricyclopentadienyltetrahydrofuranuranium(III), (η5-C5H5)3U·OC4H8, crystallizes in the centrosymmetric monoclinic space group P21/n with a 8.248(3), b 24.322(17), c 8.357(4) Å, β 101.29(5)°, V 1644.0 Å3 and ρ(calc) 2.04 g cm?1 for Z = 4 and mol.wt. 595.0. Diffraction data (Mo-Kα, 2θ(max) 45°) were collected on an Enraf-Nonius CAD4 diffractometer and the structure was refined to Rw(F) 4.7% for those 1530 reflections having I > 2σ(I). The molecule consists of a distorted tetrahedral arrangement of THF and (η5-C5H5) ligands with CpUCp angles in the range 110.4–122.4° and CpUO angles between 90.2 and 106.0°. Individual uranium-carbon distances range from 2.76(2) to 2.82(2) Å and average 2.79[1] Å. The uranium-oxygen distance of 2.551(10) Å suggests a 10-coordinate U3+ radius of 1.20 Å in this class of compounds. 相似文献
15.
Michael Laing Magriet J. Nolte Eric Singleton Erwin van der Stok 《Journal of organometallic chemistry》1978,146(1):77-86
The crystal structure of [(C8H12)6H3Me)(OC6H4Me)2} {P(OCH2)3CMe}] has been determined. a 18.32, b 18.98, c 9.35 Å, U 3251 Å3, Pn21a, Z = 4, R = 0.048, 2541 observed data.The coordination about the iridium atom is distorted trigonal bipyramidal; the two phosphorus atoms are equatorial, the σ-bonded carbon is axial, and the bidentate cyclooctadiene is bonded axialequatorial. The IrC(axial) bonds are longer than the IrC(equatorial) bonds: 2.22, 2.26; 2.17, 2.19 Å. The IrC(σ) bond length is 2.19 Å, not significantly different from the formally π-bonded C to Ir distances. The IrP lengths of 2.201 and 2.240 Å and the PIrP angle of 108.7° are normal. The longer IrP bond is in the five-membered chelate ring. The inertness to substitution is discussed. 相似文献
16.
Victor M. Ishchenko Boris M. Bulychev Grigori L. soloveichik Vitali K. Belsky Olga G. Ellert 《Polyhedron》1984,3(7):771-774
The reduction of copper (II) chloride by molybdenum and rhenium biscyclopentadienyl hydrides upon their interaction in donor-type solvents has been studied by NMR, X-ray diffraction, and magnetic methods. It is established that the ionic complex [(η5-C5H5)2Re]+[CuCl2]? forms ortho rhombic crystals with a - 13.696(2) Å, b = 7.317(1) Å, c = 5.969(1) Å, space group Pm21n, Z = 2. The cyclopentadienyl rings make a bent-sandwich with an angle between the ring centres and Re atom of 150.1°; the ClCuCl angle being 174.8° and the ReCu minimum distance 4.346(29) Å. The solution of [(η5-C5H5)2Re]+ [CuCl2]? seems to activate the CH bond of the C5H5 rings, which results in the addition of the [(C5H5)(C5H4)ReH]+ hydride ion. 相似文献
17.
β-CaNi5D0.77 is orthorhombic (a = 8.6033(13) b = 5.0810(9) c = 7.8557(15)Å, Pmcm, Z = 4, Dx = 6.48 g cm?3, V = 343.4Å3, FW = 1339.8 amu. Rietveld analysis of a neutron powder-diffraction pattern shows that D atoms occupy the centers of [Ni4Ca2] square dipyramids (“octahedra”) linked through the Ca atoms at opposite apices and forming chains. About 80% of the deuterium atoms occupy fairly regular sites (DNi = 1.53, 1.80, 1.86, 1.86 Å; DCa = 2.42, 2.45 Å). The remaining 20% occupy very distorted sites (DNi = 1.21, 1.38, 2.07, 2.07 Å; DCa = 2.54, 2.60 Å). The average DD distance in a chain is 4.3 Å. 相似文献
18.
Organomercuric compounds of the general formula and [RCOCH(R′)]2Hg, obtained from three ketones, 2,2-dimethyl 3-pentanone, 1-mesityl 1-propanone and 1-mesityl 1-ethanone, have been studied by 13C and 199Hg NMR techniques. Coupling constants J(CHg) and J(HgH) are consistent with C-metalated species; in each case the values of δ(C(2)) and J(C(2)H) observed are higher than expected for purely sp3 carbon. The contribution of O-metalated species and hyperconjugative effects are discussed. For two dioxomercuric compounds (R′ Me, R t-Bu, mesityl) the existence of diastereoisomers is suggested from 199Hg NMR data. 相似文献
19.
M.N. Bochkarev G.A. Razuvaev L.P. Maiorova N.P. Makarenko V.I. Sokolov V.V. Bashilov O.A. Reutov 《Journal of organometallic chemistry》1977,131(3):399-408
A single-crystal X-ray diffraction study of tetracarbonyl-ferra-3-cyclopentene-2,5-dione has been made. Formally the compound can be derived from maleic anhydride by substitution of the bridging oxygen by Fe(CO)4. Accordingly the bonding character is similar to that of maleic anhydride. The ironcarbon distances in the ring indicate partial double bonds. The octahedrally coordinated iron atom is linked to four terminal carbon monoxide ligands, with a longer bond distance to the equatorial than to the axial ones (FeCax 1.809 Å, FeCeq 1.854 Å). The axial CO groups are strongly inclined towards the ring (CaxFeCax 164°). The latter effect is explained by electronic repulsion of the CO groups.IR, 1H NMR, and 13C NMR data are reported. Crystal data: space groupPnama:α 12.708(10),b 10.058(7),c 7.527(5) Å;Z 4. With 625 reflections [Fo > 3o(Fo)] the structure has been refined anisotropically (hydrogen isotropically) to R0.022. 相似文献
20.
R. Mercier J.P. Malugani B. Fahys J. Douglande G. Robert 《Journal of solid state chemistry》1982,43(2):151-162
The crystalline compound Li4P2S6 is obtained either by devitrification of Li4P2S7 glass at 450°C with sulfur formation or by crystallisation at 450°C of a Li2S, P and S melt. The structure determination has been solved by X-ray diffraction on a monocrystal. The unit cell is hexagonal with a = 6.070(4), c = 6.577(4) Å, V = 209 Å3, Z = 1. Intensities were collected at 293°K with Kα (λ = 0.71069 Å) Mo radiation on an automatic Nonius CAD-4 diffractometer. The structure was solved under the assumption of random disorder of P atoms over two sites (occupancy factor of 0.5). Anisotropic least-squares refinement with W = 1 gave R = 0.047 for 90 independent reflections and 9 variables. The structure is built according to an ABAB sequence sulfur packing. Per unit cell, four out of six octahedral sites are occupied by Li ions, and the other two are statistically filled (0.5) by PP pairs. The PP central bond (2.256(13) Å) links two staggered PS3 groups (PS = 2.032(5) Å) to form the D3d symmetry P2S4?6 anion. Infrared and Raman spectra show features very similar to those of Na4P2S6, 6H2O and MIIPS3 compounds. A new assignment in terms of symmetry species is proposed for the P2S6 internal modes, which is confirmed by a normal coordinate calculation using a valence force field; the stretching force constants fPP and fPS are equal to 1.6 and 2.7 mdyne Å?1, respectively. 相似文献