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1.
Asymmetric ditertiary stibine sulfides (C 6H 5)(CH 3)(S)SbCH 2Sb(CH 3)(C 6H 5) and [(C 6H 5)(CH 3)(S)Sb] 2(CH 2) 3 have been prepared. It was found that they exist as only one of two possible diastereomers in the crystalline state. However, isomerization to the other form takes place in solution, resulting in an equilibrium mixture. A possibility of configurational lability of tertiary stibine sulfide was suggested for the first time. 相似文献
2.
The synthesis of the potential bridging ligand (C 6H 5) 2PCH 2CH 2Si(CH 3) 2C 5H 4 (3) is described. The ferrocene (6 derived from 3 has been found to form macrocyclic complexes with metal fragments NiCl 2, NiBr 2, and Co 2(CO) 6. Although monomeric, bimetallic products might have been expected based upon the reduced steric demands of ligand 3 relative to an analogous ligand, (C 6H 5) 2PCH 2Si(CH) 3) 2C 5H 4 (1), it appears that the increased flexibility in 3 is the overriding factor leading to a preference for inter- rather than intramolecular coordination of the second phosphine function in 6. 相似文献
3.
LnCl 3 (Ln=Nd, Gd) reacts with C 5H 9C 5H 4Na (or K 2C 8H 8) in THF (C 5H 9C 5H 4 = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C 5H 9C 5H 4)LnCl 2(THF) n (orC 8H 8)LnCl 2(THF) n], which further reacts with K 2C 8H 8 (or C 5H 9C 5H 4Na) in THF to form the litle complexes. If Ln=Nd the complex (C 8H 8)Nd(C 5H 9C 5H 4)(THF) 2 (a) was obtained: when Ln=Gd the 1 : 1 complex [(C 8H 8)Gd(C %H 9)(THF)][(C 8H 8)Gd(C 5H 9H 4)(THF) 2] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)2 (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η5), cyclooctatetraenyl (η8) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp′) in C5H9C5H4 group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (η5), cyclooctatetraenyl (η8) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. -0.0144 Å). 相似文献
4.
The complex (di-η 5-C 5H 4CH 2CH 2CH 2C 5H 4)Ti(η 1-C 5H 5) 2 (I) can be obtained unambiguously starting from the corresponding bridged titanocene dichloride. Attempts to synthesize the isomeric compounds (η 5-C 5H 5) 2 Ti(di-η 1-C 5H 4-CH 2CH 2CH 2C 5H 4) (I′) by the action of a convenient bridged dianion on (C 5H 5) 2 TiCl 2 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
5.
Reduction of (C 5H 5) 2TiCl 2 with Zn in presence of benzyl cyanide gives the (μ-alkyl-ideneamido)titanocene complex [(C 5H 5) 2TiCl] 2[μ-{N=C(CH 2C 6H 5)---C(CH 2C 6H 5)=N}] with C---C bond formation between two benzyl cyanide molecules. X-ray structure investigation indicates a symmetrical structure. The C=N distances are smaller than usual, the Ti---N distances are very short, and the Ti---N---C angle differs only a little from 180°, which infers a heteroallene structure of the complex. 相似文献
6.
The thermal decomposition of the complexes trans-[Pt(X)(CH 3)L 2] (L P(C 2H 5) 3; X Cl, Br, I, CN) in decalin at 170 and 200°C affords methane platinum metal and [Pt(X) 2L 2]. The kinetics of the decomposition of the complexes were determined by monitoring the appearance of methane by GLC. The observed first-order rate constant was found to be independent on the nature of the ligand X. The thermal decomposition of the trideuteriomethyl complexes [Pt(X)(CD 3)L 2] (X I, CN) in decalin- d18 at 170 and 200°C was studied by GLC/MS. The thermolysis affords CD 3H and CD 4 in ratios which are independent of the nature of X and of the temperature used. The mass spectra of the complexes were also examined. A relative scale of platinum-to-methyl bond dissociation energies has been established by measuring the appearance potential of the fragment ion [Pt(X)L 2] + and the ionization energies in the series [Pt(X)(CH 3)L 2]. Ionization potentials and PtCH 3 bond energies show a clear dependence on the nature of X which is not reflected in corresponding changes in the decomposition rates. 相似文献
7.
The crystal and molecular structure of hexaphenylditin selenide (C 6H 5) 3SnSeSn(G 6H 5) 3 was determined by X-ray diffraction data and was refined to R 0.055. The compound is monoclinic, space group P2 1, 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 SnSeC 3 tetrahedra (SeSnC angles: 104.3(5)?114.8(4)°). The bond data indicate essentially single bonds around the Sn atoms. 相似文献
8.
Crystal and molecular structures of the title compound have been determined from a three-dimensional X-ray analysis using diffractometer data. The crystals are triclinic, space group P, with Z = 2 in a unit cell of dimensions a = 11.640(1), b = 10.9139(8), c = 16.587(2) Å, α = 87.983(5), β = 99.670(6), λ = 62.250(5)°. Full matrix least squares refinement has given a final R-factor of 0.043 for 2726 reflections for which I > 2σ( I).The crystal structure consists of discrete molecules of neutral complex together with water molecules which are hydrogen bonded into pairs [O ? O separation 2.60 Å]. 0The (H 20) 2 units do not hydrogen bond to any other atoms. The ruthenium coordination is octahedral with trans carbene and isocyanide, cis iodides, and cis phosphine and carbonyl ligands. The Ru-donor distances are 2.776(2) [I trans to -PPh 3], 2.782(1) [I trans to -CO], 2.342(4) [PPh 3], 1.855(15) [CO], 2.046(15) [C(carbene)], and 1.998(16) Å [C(isocyanide)]. The bond lengths are discussed in terms of the trans effects of the ligands. The C(carbene)-N distance is 1.26(2) Å and the Ru—C(carbene)—N angle is 141.5(5)°. 相似文献
9.
en Two differnt crystal modifications of hexaphenyldigermanium sulfide (C 6H 5GeSGe(C 6H 5) 3 (I and II were obtained by crystallization from hot benzene/methanol or form ethanol at 20°C. Single crystal X-ray structural analyses for both I (low temperature data at ?130°C) and II (at 20°C) (I, R = 0.046; II, R = 0.048) were performed. I is monoclinic, P2 1/c, with a = 11.020(3), b = 15.473(3), c 18.606(3) »,π = 106.92(2)°, Z = 4; II is orthorhombic, P2 12 12 1, with a = 2.617(2), b = 17.345(3), c = 18.408(3) », Z = 4.The molecules have different conformeric structures with respect to a rotation of the (C 6H 6) 3Ge groups around the Ge bonds with very similar bond lenghts and angles. Bond data for I(II) are: GeS 2.212(1) and 2.261(1) » (2.227(2) and 2.240(2) »); GeC 1.933(4) ? 1.971(4), mean 1.945(5) » (1.931(7)?1.954(7), mean 1.943(4) »); GeSGe 111.2(1)° (110.7(1)°). The Ge bond lenghts are comparable to those in thiogermanates and do not indicate significant π-bond contributions. 相似文献
10.
The [PdCl 2(NH 2(CH 2) 5CH 3) 2] complex was tested as catalyst for 1-heptyne semihydrogenation under mild conditions of temperature and pressure in homogeneous
and heterogeneous systems. Species were characterized by XPS and FTIR techniques.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
11.
Heat-capacity measurements have been made in the temperature range 110 to 300 K. In the range 160 to 240 K the chromocene curve shows an anomaly related to an order-disorder phase transition in the solid. On the other hand the dibenzene chromium curve indicates no phase transition and is in accordance with an ordered structure at room temperature. 相似文献
12.
Reaction of YbI 2 with two equivalents of cyclopentylindenyl lithium (C 5H 9C 9H 6Li) affords ytterbium(II) substituted indenyl complex (C 5H 9C 9H 6) 2Yb(THF) 2 (1) which shows high activity to ring-opening polymerization (ROP) of lactones. The reaction between YbI 2 and cyclopentylcyclopentadienyl sodium (C 5H 9C 5H 4Na) gives complex [(C 5H 9C 5H 4) 2Yb(THF)] 2O 2 (2) in the presence of a trace amount of O 2, the molecular structure of which comprises two (C 5H 9C 5H 4) 2Yb(THF) bridged by an asymmetric O 2 unit. The O 2 unit and ytterbium atoms define a plane that contains a Ci symmetry center. 相似文献
13.
The complex dicarbonylbis(diphenylethylphosphine)platinum, Pt(CO) 2[P(C 6H 5) 2(C 2H 5)] 2, crystallizes in either of the enantiomorphous space groups P3 121 (No. 152) and P3 221 (No. 154) with cell dimensions a = 10.64(1), c = 22.06(1) Å, U = 2163 Å 3; pc = 1.564 g/cm 3 for Z = 3, pm = 1.55(3) g/cm 3. The intensities of 1177 independent reflections have been determined by counter methods with MoKα monochromatized radiation. The structure has been solved by the heavy atom method. The refinement, carried out by full-matrix least squares down to a final R factor of 0.042, has enabled the absolute configuration of the crystal sample (space group P3 121) to be ascertained. The molecule is roughly tetrahedral, and has the metal atom lying on a two-fold axis of the cell. Bond parameters are: PtC = 1.92(2) Å, PtP = 2.360(4) Å, CPtC = 117(1)° and PPtP = 97.9(2)°. The PtC 2 and PtP 2 moieties make a dihedral angle of 86.0(3)°. The overall C2 symmetry of the molecule is probably only a statistically averaged situation, a disorder in the PtCO interactions being apparent from the orientations of the thermal ellipsoids of the C and O atoms. 相似文献
14.
The tridentate chelate ligand bis(diphenylphosphinopropyl) amine and its title complex were prepared and characterized by 31P n.m.r. and other spectroscopic data. Its activation energy E A for hydrogenation of cyclohexene is 52.3 kJ mol –1.
31P. 52,3 /. 相似文献
15.
1-Allyl-4-aminopyridinium chloride reacts with Cu(NO 3) 2 · 3H 2O in an ethanolic solution under the conditions of ac electrochemical synthesis at copper electrodes to form crystals of compound
[(NH 2C 5H 4N(C 3H 5)) 2Cu 3Cl 3(NO 3) 2] ( I). The crystals of compound I are monoclinic: space group P2 1/ c, Z = 4, a = 25.770(7), b = 7.230(4), c = 12.505(5) ?, β = 92.58(3)°, V = 2328(2) ? 3. The direct interaction of 1-allylquinolinium nitrate with Cu(NO 3) 2 · 3H 2O in a methanolic solution in the presence of metallic copper yields crystals of compound [C 9H 7N(C 3H 5)Cu(NO 3) 2] ( II). The crystals of compound II are triclinic: space group P
, a = 6.756(3), b = 8.391(4), c = 12.489(5) ?, α = 77.18(3)°, β = 89.48(4)°, γ = 73.32(3)°, V = 662.0(5) ? 3. The structure of compound I is built of infinite linear anions: polymeric fragments {(NH 2C 5H 4N(C 3H 5)) 2Cu 3Cl 3(NO 3) 2}
n
. Each of two copper atoms (Cu(1) and Cu(2)) π-coordinates the C=C bonds of the allyl groups of the 1-allyl-4-aminopyridinium
cations, the oxygen atom of the nitrate ions, and two chlorine atoms. The third copper atom Cu(3) is linearly linked with
two chlorine atoms. Particular polymeric fragments are additionally joined by the N-H…O, C-H…O, C-H…Cl hydrogen bonds. The
crystal structure of compound II is built-up of the isolated L 2Cu 2(NO 3) 4 fragments (L is the 1-allylquinolinium cation). The metal atom is localized in the trigonal pyramidal coordination environment
of three oxygen atoms of the nitrate ions and of the C=C bond of the allyl group of the cation. The particular L 2Cu 2(NO 3) 4 fragments are additionally joined by the C-H…O hydrogen bonds.
Original Russian Text ? A.V. Pavlyuk, T. Lis, M.G. Mys’kiv, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No.
6, pp. 458–462. 相似文献
16.
A kinetic study of the reaction of hydroxide ion with (CO) 5MoC(XCH 2CH 2OH)(C 6H 5) (X = O for Mo-OR, and X = S for Mo-SR), and (CO) 5WC(OCH 2CH 2OH)(C 6H 4-Z) ( W-OR(Z)) is reported. The results are consistent with a pathway in basic solution that involves rapid deprotonation of the OH group followed by rate-limiting cyclization. The parameter k1KOH for the reaction of W-OR(Z) was determined as a function of the phenyl substituents. They were found to correlate well with the Hammett equation. The dependence of the reactivity on the metal atoms in the complexes M-OR (M = Cr, Mo and W) shows that the reactivity decreases slightly down the group of the Periodic Table, while for M-SR the reactivity increases slightly down the group. A plausible explanation of these results is offered based on electronegativity values of the metal atoms. The much higher ρ( k1KOH) value for W-OR(Z) over W-SR(Z) arises mainly due to the stabilization of the reactant carbene complex by the stronger π-donor effect of oxygen over sulfur. 相似文献
17.
Syntheses and single-crystal X-ray diffraction studies have been completed on two cycloruthenapentadienyl (CO) 6Ru 2L 2 derivatives, with L = CH 2OHC = CCH 2OH and C 2H 5C=CCH 2CH 2OH respectively. Crystal data are as follows: for [(CO) 3RuC 4(CH 2OH) 4]Ru(CO) 3·H 2O, P2 1/ c, a 13.72(1), b 9.501(4), c 14.86(1) Å, β 101.10(6)°, Rw = 0.052 for 1911 reflections; for [(CO) 3RuC 4(CH 2CH 2OH) 2(C 2H 5) 2]Ru(CO) 3, P2 1/ c, a 9.191(3), b 16.732(4), c 14.903(3) Å, β 113.61(4)°, Rw = 0.042 for 2865 reflections. Both compounds are built up from binuclear units, each unit being regarded as a Ru(CO) 3 fragment π-bonded to a cycloruthenapentadienyl ring. The molecular parameters are compared with those of known cyclometallapentadienyl complexes of transition metals. The presence of a semi-bridging CO group is discussed. 相似文献
18.
The crystal and molecular structure of the complex Th[η 5-(CH 3) 5C 5] 2[CH 2-Si(CH 3) 3] 2, which undergoes facile intramolecular cyclometalation to the thoracyclobutane Th[η 5-(CH 3) 5C 5] 2(CH 2) 2Si(CH 3) 2, is reported. While the Th[η 5-(CH 3) 5C 5] 2 ligation is unexceptional, the Th[CH 2Si(CH 3) 3] 2 fragment is highly unsymmetrical having Th-C (corresponding angle Th-C-Si) 2.51(1) Å (132.0(6)°) and 2.46(1) Å (148.0(7)°). This conformation, which appears to result from severe intramolecular non-bonded contacts, allows a methyl hydrogen atom of one CH 2Si(CH 3) 3 ligand to approach within ca. 2.3 Å of the α-carbon atom of the other CH 2Si(CH 3) 3 ligand. 相似文献
19.
The thermolysis of the complexes [Co(NH 3) 6] 2C 2O 4[Cu(C 2O 4) 2] 2 (I) and [Co(NH 3) 6]Cl[Cu(C 7H 4O 3) 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
20.
Two silyl-zirconium compounds (η-C 5H 5) 2ZrCl[Si(CH 3) 3] (I) and (η-C 5H 5) 2-Zr[Si(CH 3) 3] 2 (II), have been prepared by the reaction of (η-C 5H 5) 2ZrCl 2 with Hg[Si(CH 3) 3] 2 in refluxing benzene. While I is unreactive toward 1-hexyne (55–60°C) and CO (350 psi), the zirconiumsilicon bond is cleaved by electrophiles such as Cl 2, HgCl 2, and AlCl 3. 相似文献
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