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1.
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
2.
Thermal displacement of coordinated nitriles RCN (R = CH 3, C 2H 5 or n-C 3H 7) in [C 5H 5Fe(L 2)(NCR)]X complexes (L 2 = P(OCH 3) 3) 2, (P(OC 6H 5) 3) 2 or (C 6H 5) 2PC 2H 4P(C 6H 5) 2 (DPPE)) by E(CH 3) 2 affords high yields of [C 5H 5Fe(L 2)(E(CH 3) 2)]X compounds (E = S, Se and Te; X = BF 4 or PF 6). Spectroscopic data and ligand displacement reactions are presented and discussed together with related observations on [C 5H 5Fe(CO) 2(E(CH 3) 2)]BF 4 compounds. The molecular structure of [C 5H 5Fe(P(OCH 3) 3) 2(S(CH 3) 2)]PF 6 was determined by a single-crystal X-ray diffraction study: monoclinic, space group P2 1/ 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
3.
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
4.
The ruthenium(II) complex Ru(CO) 2(NH 2(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I has been prepared by the reaction of Ru(CO) 4(Si(C 6H 5)(CH 3) 2)I with benzylamine. Two-dimensional homonuclear 1H NMR experiments examine the scalar coupling of the enantiotopic amino and methylene protons of the benzylamine ligand. X-ray analysis of Ru(CO) 2(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I·1/3C 5H 12 (triclinic; P
; a = 14.266(4), b = 15.748(5), c = 20.082(6) Å; = 94.38(3), β = 96.30(2), γ = 101.52(2)°) indicates three crystallographically unique complexes form a clathrate with a pentane guest. 相似文献
5.
Three families of heterobimetallic compounds were obtained by reaction of [Mo(CO) 3(CH 3CN) 2(Cl)(SnRCl 2)] (R = Ph, Me) with P(4-XC 6H 4) 3 (X = Cl, F, H, Me, MeO). The type of compound obtained dependent on the solvent and concentration of the starting compound. So, [Mo(CO) 2(CH 3COCH 3) 2(PPh 3)(Cl)(SnRCl 2)]· nCH 3COCH 3 (R = Ph, n = 0.5; R = Me, n = 1) (type I) and [Mo(CO) 3{P(4-XC 6H 4) 3}(μ-Cl)(SnRCl 2)] 2 (R = Ph, X = Cl, F, H, Me, MeO; R = Me, X = Cl, F) (type II) were isolated from acetone solution in ca 0.05 M and 0.1 M concentrations, respectively. However, [Mo(CO) 3(CH 3CN) {P(4-XC 6H 4) 3}(Cl)(SnRCl 2)] (R = Ph, X = H; R = Me, X = Cl, F, H) (type III) were obtained from dichloromethane solution independently of the concentration used. All new complexes showed a seven-coordinate environment at molybdenum, containing Mo---Cl and Mo---Sn bonds. Mössbauer spectra indicated a four-coordination at tin for type III complexes. 相似文献
6.
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
7.
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
8.
Reaction of ansa-cyclopentadienyl pyrrolyl ligand (C 5H 5)CH 2(2-C 4H 3NH) (2) with Ti(NMe 2) 4 affords bis(dimethylamido)titanium complex [(η 5-C 5H 4)CH 2(2-C 4H 3N)]Ti(NMe 2) 2 (3) via amine elimination. A cyclopentadiene ligand with two pendant pyrrolyl arms, a mixture of 1,3- and 1,4-{CH 2(2-C 4H 3NH)} 2C 5H 4 (4), undergoes an analogous reaction with Ti(NMe 2) 4 to give [1,3-{CH 2(2-C 4H 3N)} 2(η 5-C 5H 3)]Ti(NMe 2) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies. 相似文献
9.
The η 3-allyliridium complexes [Ir(η 3-2-RC 3H 4)(P iPr 3) 2] (2, 3) have been prepared in a one-pot reaction from [IrCl(C 2H 4) 2] 2, 2-RC 3H 4Li and P iPr 3 in 70% yield. Compounds 2 and 3 react spontaneously with H 2 to give [IrH 5(P iPr 3) 2] (7) and with excess PhC=CH and MeCCH to give [Ir(CCPh) 3(P iPr 3) 2] (5) and [Ir(CCMe) 2(CMe=CH 2)(P iPr 3) 2] (6), respectively. From 2 (or 3) and two equivalents of PhCCH the complex [IrH(CCPh) 2(P iPr 3) 2] (4) has been obtained. Treatment of 2 or 3 with CF 3CO 2H does not lead to a cleavage of the allyl-metal bond but affords the allyl(hydrido)-iridium(III) complexes [IrH(η 3-2-RC 3H 4)(η 1-P 2CCF 3)(P iPr 3) 2] (8, 9) in almost quantitative yield. 相似文献
10.
A kinetic study of the oxidative addition of RC 6H 4CN (R = H, m-CN, p-CN) to Ni(DEPB) 2 (DEPB = 1,4-bis(diethylphosphino)butane) suggests a template mechanism leading to the fission of one C---CN bond. The reaction products are trans-planar cyano-organonickel(II) complexes, Ni 2(μ-DEPB) 2(RC 6H 4) 2(CN) 2 and Ni(η 1- DEPB)(RC 6H 4)(CN), in equilibrium. through exchange of DEPB. 相似文献
11.
An unexpected trimanganese(I) tetrathiolate-bridged complex, [Mn 3(CO) 9(μ-SC 6H 5) 4] −, with an incomplete cubane structure, was obtained by thermal reaction of [Mn 2(CO) 10] with [Mo(η 5-C 5H 5) 2(SC 6H 5) 2]. The structure, established by single-crystal X-ray diffraction studies, shows the cation, [Mo(η 5-C 5H 5) 2(H)CO] +, directed towards the vacant site of the cubane structure. Possible routes by which the anion and the cation could be formed are discussed. 相似文献
12.
The sterically hindered zinc chalcogenolato complexes [Zn(EAr″) 2] 2 (E = S, Se; Ar″ = 2,4,6-Bu t3C 6H 2) react with 1 equivalent of tert-butylisocyanide in non-coordinating solvents to give Zn(EC 6H 2Bu t3) 2(CNBu t) (1, E = S; 2, E = Se) as thermally stable crystalline adducts; the compounds are thought to be chalcogenolato-bridged dimers. In the presence of excess isocyanide ligand the 1 : 2 adducts Zn(EAr″) 2(CNBu t) 2 (3, E = S; 4, E = Se) are isolated. The compounds represent the first examples of well-characterized isocyanide complexes of zinc. The X-ray structure of 4 showed that it is monomeric with a distorted tetrahedral coordination geometry of the metal centre, which reflects the steric requirements of the chalcogenolato and isocyanide ligands, respectively. 相似文献
13.
Reaction of C 5H 4(SiMe 3) 2 with Mo(CO) 6 yielded [(η 5-C 5H 3(SiMe 3) 2)Mo(CO) 3] 2, which on addition of iodine gave [(η 5-C 5H 3(SiMe 3) 2Mo(CO) 3I]. Carbonyl displacement by a range of ligands: [L = P(OMe) 3, P(OPr i) 3,P(O- o-tol) 3, PMe 3, PMe 2Ph, PMePh 2, PPh 3, P( m-tol) 3] gave the new complexes [(η 5-C 5H 3(SiMe 3) 2 MO(CO) 2(L)I]. For all the trans isomer was the dominant, if not exclusive, isomer formed in the reaction. An NOE spectral analysis of [(η 5-C 5H 3(SiMe 3) 2)Mo(CO) 2(L)I] L = PMe 2Ph, P(OMe) 3] revealed that the L group resided on the sterically uncongested side of the cyclopentadienyl ligand and that the ligand did not access the congested side of the molecule. Quantification of this phenomenon [L = P(OMe) 3] was achieved by means of the vertex angle of overlap methodology. This methodology revealed a steric preference with the trans isomer (less congestion of CO than I with an SiMe 3 group) being the more stable isomer for L = P(OMe) 3. 相似文献
14.
The compounds (π-C 5H 5)(CO) 2LM-X (L = CO, PR 3; M = Mo, W; X = BF 4, PF 6, AsF 6, SbF 6) react with H 2S, p-MeC 6H 4SH, Ph 2S and Ph 2SO(L′) to give ionic complexes [(π-C 5H 5)(CO) 2LML′] + X −. Also sulfur-bridged complexes, [(π-C 5H 5)(CO) 3W---SH---W(CO) 3(π-C 5H 5)] + AsF 6− and [(π-C 5H 5)(CO) 3M-μ-S 2C=NCH 2Ph-M(CO) 3(π-C 5H 5)], have been obtained. Reactions with SO 2 and CS 2 have been examined. 相似文献
15.
The electron donating water soluble phosphines, P{(CH 2) nC 6H 4- p-SO 3Na} 3, n = 1, 2, 3 and 6, react rapidly with Co 2(CO) 8 under two phase reaction conditions to yield the disproportionation products, [Co(CO) 3(P{(CH 2) nC 6H 4- p-SO 3Na 3} 2] [Co(CO) 4]. Selective precipitation yields the formally zwitterionic complex anions as the sodium salt, [Co(CO) 3(P{(CH 2) nC 6H 4- p-SO 3} 3) 2] 5−. The anions can be used as precursors to water soluble cobalt hydroformylation catalysts under two phase and supported aqueous phase conditions. The tendency to form alcohol products is low with these complexes. The behavior of the catalysts is consistent with an active species that remains water soluble during the reaction and is not leached into the nonaqueous phase. 相似文献
16.
The reactions of the half-sandwich molybdenum(III) complexes CpMo(η 4-C 4H 4R 2)(CH 3) 2, where Cp=η 5-C 5H 5 and R=H or CH 3, with equimolar amounts of B(C 6F 5) 3 have been investigated in toluene. EPR monitoring shows the formation of an addition product which does not readily react with Lewis bases such as ethylene, pyridine, or PMe 3. The analysis of the EPR properties and the X-ray structure of a decomposition product obtained from dichloromethane, [CpMo(η 4-C 4H 6)(μ-Cl)(μ-CH 2)(O)MoCp][CH 3B(C 6F 5) 3], indicate that the borane attack has occurred at the methyl position. 相似文献
17.
The reaction between RMgCl (two equivalents) and 1,2-W 2Cl 2(NMe 2) 4 in hydrocarbon solvents affords the compounds W 2R 2(NMe 2) 4, where R = allyl and 1− and 2-methyl-allyl. In the solid state the molecular structure of W 2(C 3H 5) 2(NMe 2) 4 has C2 symmetry with bridging allyl ligands and terminal W---NMe 2 ligands. The W---W distance 2.480(1) Å and the C---C distances, 1.47(1) Å, imply an extensive mixing of the allyl π-MOs with the WW π-MOs, and this is supported by an MO calculation on the molecule W 2(C 3H 5) 2(NH 2) 4 employing the method of Fenske and Hall. The most notable interaction is the ability of the (WW) 6+ centre to donate to the allyl π *-MO (π 3). This interaction is largely responsible for the long W---W distance, as well as the long C---C distances, in the allyl ligand. The structure of the 2-methyl-allyl derivative W 2(C 4H 7) 2(NMe 2) 4 in the solid state reveals a gauche-W 2C 2N 4 core with W---W = 2.286(1) Å and W---C = 2.18(1) Å, typical of WW and W---C triple and single bonds, respectively. In solution (toluene-d 8) 1H and 13C NMR spectra over a temperature range −80°C to +60°C indicate that both anti- and gauche- W 2C 2N 4 rotamers are present for the 2-methyl-allyl derivative. In addition, there is a facile fluxional process that equilibrates both ends of the 2-methyl-allyl ligand on the NMR time-scale. This process leads to a coalescence at 100°C and is believed to take place via an η 3-bound intermediate. The 1-methyl-allyl derivative also binds in an η 1 fashion in solution and temperature-dependent rotations about the W---N, W---C and C=C bonds are frozen out at low temperatures. The spectra of the allyl compound W 2(C 3H 5) 2(NMe 2) 4 revealed the presence of two isomers in solution—one of which can be readily reconciled with the presence of the bridging isomer found in the solid state while the other is proposed to be W 2(η 3-C 3H 5) 2(NMe 2) 4. The compound W 2R 2(NMe 2) 4 where R = 2,4-dimethyl- pentadiene was similarly prepared and displayed dynamic NMR behaviour explainable in terms of facile η 1 = η 3 interconversions. 相似文献
18.
[1,8-C 10H 6(NR) 2]TiCl 2 (3; R=SiMe 3, Si iBuMe 2, Si iPr 3) complexes have been prepared from dilithio salts [1,8-C 10H 6(NR) 2]Li 2 (2) and TiCl 4 in diethyl ether in moderate yields (60–63%). These complexes showed significant catalytic activities for ethylene polymerization and for ethylene/1-hexene copolymerization in the presence of methylaluminoxane (MAO), methyl isobutyl aluminoxane (MMAO), Al iBu 3– or AlEt 3–Ph 3CB(C 6F 5) 4 as a cocatalyst. The catalytic activities performed in heptane (cocatalyst MMAO) were higher than those carried out in toluene (cocatalyst MAO): 709 kg-PE/mol-Ti·h could be attained for ethylene polymerization by using [1,8-C 10H 6(NSi iBuMe 2) 2]TiCl 2–MMAO catalyst system. 相似文献
19.
The singlet-triplet separations for the edge-sharing bioctahedral (ESBO) complex W 2(μ-H)(μ-Cl)(Cl 4(μ-dppm) 2 · (THF) 3 (II) has been studied by 31P NMR spectroscopy. The structural characterization of [W 2(μ-H) 2(μ-O 2CC 6H 5) 2Cl 2(P(C 6H 5) 3) 2] (I) by single-crystal X-ray crystallography has allowed the comparison of the energy of the HOMOLUMO separation determined using the Fenske-Hall method for a series of ESBO complexes with two hydride bridging atoms, two chloride bridging atoms and the mixed case with a chloride and hydride bridging atom. The complex representing the mixed case, [W 2(μ-H)(μ-Cl)Cl 4(μ-dppm) 2 · (THF) 3] (II), has been synthesized and the value of −2 J determined from variable-temperature 31P NMR spectroscopy. 相似文献
20.
The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh 3) 2] (Ar = C 6H 5, C 6F 5, 2-C 6H 4CH 3, 3-C 6H 4CH 3, 4-C 6H 4CH 3, 2-C 6H 4OCH 3, 2,6-C 6H 3-(OCH 3) 2, 4-C 6H 4N(CH 3) 2, 3-C 6H 4Cl, 4-C 6H 4Cl, 4-C 6H 4Cl, 3-C 6H 4CF 3, 4-C 6H 4CF 3) are described, and the most important IR data as well as the 31P NMR parameters of these, without exception trans-planar, compounds are given. Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O2)(CO)(PPh3)2] (Ar = C6H5, 3-C6H4CH3, 4-C6H4CH3). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO2 the similar irreversible addition compound [Ir(4-C6H4CH3)-(SO2)(CO)(PPh3)2] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed. The first step of the reaction between [Ir(4-C6H4CH3)(CO)(PPh3)2] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C6-H4CH3)(CO)(PPh3)2]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature. 相似文献
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