共查询到20条相似文献,搜索用时 15 毫秒
1.
A. A. Pasynskii I. V. Skabitskii S. S. Shapovalov A. R. Galustyan Yu. V. Torubaev Zh. V. Dobrokhotova V. A. Grinberg E. V. Mutseneck A. R. Kudinov 《Russian Chemical Bulletin》2007,56(9):1731-1735
The reaction of Cb*Co(CO)2I (1) (Cb* is tetramethylcyclobutadiene) with sodium phenyltelluride afforded the mononuclesar complex Cb*Co(CO)2TePh (2). The reaction of the latter with W(CO)5(THF) produced the Cb*Co(CO)2TePh[W(CO)5] compound (4). The reaction of 1 with the Cp2Cr2(SCMe3)2S complex gave the heterometallic cluster Cb*Co(μ3-S)2Cr2Cp2 (μ-SCMe3) (5). Complexes 2, 4, and 5 are diamagnetic. Their structures were determined by X-ray diffraction. Complex 2 contains the Co-Te bond (2.585(1) Å); complex 4, the Co-Te (2.558(8) Å) and W-Te (2.8467(6) Å) bonds. Complex 5 has the stable triangular sulfide-and tert-butylmercaptide-bridged core Cr2Co (Cr-Cr and Cr-Co bond lengths are 2.626(2) and 2.673(2) Å, respectively) with Cp ligands at the chromium atoms and a Cb* ligand at the cobalt atom. Complex 5 was characterized by cyclic voltammetry. The thermolysis of complex 4 was studied. 相似文献
2.
《Journal of organometallic chemistry》1986,299(1):111-118
The electrochemical reductive acylation of (benzophenone)Cr(CO)3 and (benzophenone) [Cr(CO)3]2 has been performed in DMF, by electrochemical reduction of complexed ketones in the presence of acetic and benzoic anhydride in excess. Three complexed benzhydryl esters ArCH(OCOR)PhCr(CO)3, (Ar = Ph, R = Me: Ar = PhCr(CO)3, R = Me; Ar = PhCr(CO)3, R = Ph) were obtained in 46–57.5% yields after purification. Electrochemical reduction of (diphenylmethane)Cr(CO)3 in the presence of acetic anhydride in excess leads to m-benzyl acetophenone. 相似文献
3.
4.
《Polyhedron》2001,20(9-10):1107-1113
The reactions of dipropargyl manolate and terephthalate, respectively, with Co2(CO)8 in THF at room temperature gave four new compounds [R(CO2CH2C2H-μ)2][Co2(CO)6]2 (R=CH2, 1a; R=C6H4, 1b) and [(HC2CH2OCO)R(CO2CH2C2H-μ)][Co2(CO)6] (R=CH2, 2a; R=C6H4-1,4-, 2b), and compounds 2a and b reacted with RuCo2(CO)11 to form two new linked clusters [R(CO2CH2C2H-μ)2][Co2(CO)6][RuCo2(CO)9] (R=CH2, 3a; R=C6H4-1,4-, 3b). The treatment of two dipropargyl esters, respectively, with RuCo2(CO)11 afforded another two new clusters [R(CO2CH2C2H-μ)2][RuCo2(CO)9]2 (R=CH2, 4a; R=C6H4-1,4-, 4b). The reactions of dipropargyl manolate, terephalate with Mo2Cp2(CO)4 gave rise to the formation of dinuclear complexes [(HC2CH2OCO)R(CO2CH2C2H-μ)][Mo2Cp2(CO)4] (R=CH2, 5a; R=C6H4-1,4-, 5b), compound 5a reacted with Co2(CO)8 to produce the cluster [CH2(CO2CH2C2H-μ)2][Co2(CO)6][Mo2Cp2(CO)4] 6a. All the new clusters have been characterized by C/H elemental analysis, IR and 1H NMR spectroscopies. The structure of [CH2(CO2CH2C2H-μ)2][Co2(CO)6]2 1a and [p-(HC2CH2OCO)C6H4(CO2CH2C2H-μ)][Co2(CO)6] 2b have been determined by single crystal X-ray diffraction methods. 相似文献
5.
Abstarct The Cp)2Ni2Fe(CO)3(µ3-C2H2) and Cp)2Ni2Fe(CO)3(µ3-C2H2) (B) complexes have been synthesized and spectroscopically characterized. An accurate X-ray study and a comparison with related structures shows that the substituents of the alkyne ligands exert considerable effects on the bonding parameters.Crystal data for complex A, monoclinic space group P21/n,a = 8.418(1),b = 15.779(2),c = 14,493(1) Å, = 91.64(1)°,Z = 4, 2753 observed reflections,R = 0.022; crystal data for complex B, monoclinic space group C2/c,a = 16.2189(7),b = 7.445(3),c = 25.745(5) Å, = 103.74(3),Z=8, 1853 observed reflections,R = 0.051. 相似文献
6.
《Journal of organometallic chemistry》1992,439(1):C16-C19
The reaction of the secondary metallo-phosphanes Cp(CO)2(L)W-PH(Mes) (L CO, PMe3) (1a,b) with the iron complex [Cp(CO)3Fe]BF4 (2) or Cp(CO)2Fe-I (3), respectively, affords the ferrio(wolframio)phosphonium salts [Cp(CO)2(L)W-P(Mes)-Fe(CO)2Cp]X (X I (4a), BF4 (4b). Deprotonation of 4a, b with DBU results, in both cases, in the selective formation of a WP bond owing to additional CO- or Me3P-elimination to give the phosphinidene complex Cp(CO)2WP(Mes)-Fe(CO)2Cp (6). 相似文献
7.
《Journal of organometallic chemistry》1994,464(1):71-76
The reaction of Cr(CO)3(NH3)3 with diphenylacetylene affords as a main product the complex with Cr(CO)3 moiety bound to a phenyl ring of diphenylacetylene; Cr(CO)3(η6-PhC2Ph) (I). Complex I readily reacts with Co2(CO)8 yielding the mixed metal complex Cr(CO)3(η6:η2-PhC2Ph)Co2(CO)6 (II). The reaction proceeds with retention of the Cr(CO)3 (η6-arene) structural unit, the Co2(CO)6 fragment being bound to the triple bond of diphenylacetylene in μ2,η2-mode. The structure of II was determined by single crystal X-ray analysis. The complex crystallizes in space group P21/c with unit cell parameters a 8.666(3) Å, b 18.046(3) Å, c 15.155(6) Å. β 97.57(3)°, V 2349(2) Å3, Z = 4, Dx = 1.70 g/cm3. The structure was solved by direct methods and refined by full-matrix least-squares technique to R and Rw values of 0.032 and 0.034, respectively, for 3655 observed reflections. The data obtained show that two structural units in II, Cr(CO)3(η6-Ph-) and Co2(CO)6(μ2,η2-CC), are distorted due to steric repulsion between these metal carbonyl moieties. The Cr(CO)3 fragment is shifted from the centre of the phenyl ring and slightly tilted with respect to the phenyl ring plane. The Co2C2 tetrahedron in the Co2(CO)6(μ2,η2-CC) moiety is distorted in such a way that two of the four CoiCj bonds are elongated. 相似文献
8.
9.
T. Nagata H. Yoshida T. Kondow 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1993,26(1):367-369
Photoelectron spectra of (CO2)nH2O? (2≤n≤8) and (CO2)n(H2O) 2 ? (1≤n≤2) were measured at the photon energy of 3.49 eV. The spectra show unresolved broad features, which are approximated by Gaussians. The vertical detachment energies (VDEs) were determined as a function of the cluster size. For (CO2)nH2O?, the VDE-n plots exhibit a sharp discontinuity between n=3 and 4; the VDE value is ≈3.5 eV at n=3, while it drops down abruptly to 2.59 eV at n=4. This discontinuity in VDE is ascribed to "core switching" at n=4; a C2O 4 ? dimer anion forms the core of (CO2)nH2O? for n≤3, while a monomer CO 2 ? is the core for n≥4. The (CO2)2(H2O) 2 ? ion has a VDE of 2.33 eV, indicating the presence of a CO 2 ? monomer core in the binary clusters containing two H2O molecules. 相似文献
10.
Summary Quantum chemical calculations based on density functional theory have been performed on Cr(CO)6, (6-C6H6)Cr(CO)3 and (6-C6H6)Cr(CO)2(CS) at the local and nonlocal level of theory using different functionals. Good agreement is obtained with experiment for both optimized geometries and metal-ligand binding energies. In particular, a comparison of metal-arene bond energies calculated for the (6-C6H6)Cr(CO)3 and (6-C6H6)Cr(CO)2(CS) complexes correlates well with kinetic data demonstrating that substitution of one CO group by CS leads to an important labilizing effect of this bond, which may be primarily attributed to a larger -backbonding charge transfer to the CS ligand as compared with CO. 相似文献
11.
Reaction of [Y(BDI)(I)2(THF)] (1) with two equivalents of Na[Cr(Cp)(CO)3] affords the dimeric complex [{Y(BDI)[Cr(Cp)(CO)3]2(THF)}2] (2). Complex 2 contains two yttrium-BDI units which are each linked by two isocarbonyl bridging [Cr(Cp)(CO)3]? anions; a terminal, isocarbonyl bound [Cr(Cp)(CO)3]? anion and THF molecule completes the coordination sphere at each yttrium. This results in formation of a centrosymmetric, 12-membered C4O4Cr2Y2 ring. Forcing conditions were required to produce carbonyl metallate derivatives such as 2, as exemplified by the isolation of crystals of [W(Cp)(CO)3][Na(THF)2] (3) from the analogous reaction between 1 and two equivalents of Na[W(Cp)(CO)3]. Complex 3 loses coordinated THF very easily and all isolated samples exhibit spectra consistent with the known, un-solvated form of Na[W(Cp)(CO)3]. The crystal structure of 3 shows dimeric sodium units bridged by two THF molecules and one isocarbonyl group. Each sodium centre is further coordinated by one THF molecule and two isocarbonyl ligands. There are two crystallographically distinct [W(Cp)(CO)3]? units; one exhibits two bridging isocarbonyl groups and the other exhibits three bridging isocarbonyl groups to different sodium dimer units. This results in a 2-dimensional polymeric sheet network in the solid state. Complex 2 was characterised by single crystal X-ray diffraction, NMR spectroscopy, FTIR spectroscopy and CHN microanalysis; complex 3 was characterised by single crystal X-ray diffraction only. 相似文献
12.
Xu Feng Chen Yong-Mei Yang Shi-Yan Sun Wen-Hua Yu Kai-Bei 《Transition Metal Chemistry》2000,25(1):108-111
CpMoFeCo(CO)7(3-S) reacts with Cp*M(CO)3Cl or CpM(CO)3Cl (M=W, Mo) to gave the mixed-metal clusters Cp*WCpMoFe(CO)7(3-S) (1), Cp*MoCpMoFe(CO)7(3-S) (2), CpWCp*MoFe(CO)7(3-S) (3), CpMoCp*MoFe(CO)7(3-S) (4) and Cp*WCp*MoFe(CO)7(3-S) (5). The title clusters have been characterized by i.r., 1H/13C-n.m.r. spectroscopy and their compositions have been confirmed by elemental analyses. The X-ray crystal structure analysis shows the two independent enantiomeric molecules of clusters (1) in one crystal structure unit. 相似文献
13.
14.
《Journal of organometallic chemistry》1987,321(1):51-66
The reaction of bis(di-t-butylphosphino) sulphur diimide, S(NPtBu2)2 (1) 1, with coordinatively unsaturated 16-electron complex fragments [M(CO)5] leads to both binuclear 1 : 2 adducts S{NPtBu2[M(CO)5]}2 (M = Cr (2B), Mo (3B) and W (4B)) and mononuclear chelate complexes S(NPtBu2)2M(CO)4 (M = Cr (2C), Mo (3C) and W (4C)). A binuclear compound S{NPtBu2[Fe(CO)4]}2 (5B) is obtained from the reaction of 1 with Fe2(CO)9. The new complexes which all contain the intact sulphyr diimide 1 are characterized on the basis of their infrared, 1H, 13C and 31P NMR spectra. An X-ray structure analysis of S(NPtBu2)2Cr(CO)4 (2C) reveals a distorted octahedral coordination sphere around the central chromium atom and an almost planar but twisted six-membered Cr(PN)2S heterocycle with angles of 91.98(2)° at chromium (P(1)CrP(2)) and 124.6(1)° at sulphur (N(1)SN(2)). 相似文献
15.
《Journal of organometallic chemistry》1987,319(3):C45-C50
(η4-Tropone)Fe(CO)3 and (η4-isoprene)Fe(CO)3 form separable diastereoisomers on substitution of CO by (+)-(neomenthyl)PPh2. In the tropone complex, diastereoisomer interconversion occurs by a 1,3-metal shift. The absolute configuration of the isoprene complex has been determined crystallographically. 相似文献
16.
室温下,对苯二甲酸二丙炔醇酯分别与Co2(CO)8,Mo2Cp2(CO)4和RuCo2(CO)11反应,得到三个有机金属化合物[C6H4-p-(CO2CH2C2H-μ)2][Co2(CO)6]2(1)、[C6H4-p-(CO2CH2C2H)2][RuCo2(CO)9]2(2)和[(HC2CH2OCO)C6H4-p-(CO2CH2C2H-μ)][Mo2Cp2(CO)4](3).研究发现三种金属核对端炔氢的屏蔽作用依次为RuCo2(CO)9>Co2(CO)6>Mo2(CO)4Cp2.化合物1的晶体衍射发现,属三斜晶系,空间群PT,a=8.139(2)A,b=8.808(3)A,c=1 1.343(3)A,β=96.260(6)°,V=773.4(4)A3,Z=1,Dc=1.748g@cm-3,R=0.0513,wR=0.1266. 相似文献
17.
18.
Two [Cr(C2O4)2(AB)]2– type complexes, obtained from the reaction of cis-[Cr(C2O4)2(H2O)2]– with the AB ligand, [AB = picolinic (pyac) or 2-pyridine-ethanoic acid (pyeac) anions], were converted into [Cr(C2O4)(pyac)(H2O)2]0 and [Cr(C2O4)(pyeac)(H2O)2]0 compounds, respectively via FeIII-induced substitution of the oxalato ligand. The aquation products were separated chromatographically and their spectral characteristics and acid dissociation constants determined. The kinetics of the oxalato ligand substitution were studied with a 10–40 fold excess of FeIII over [CrIII] at [H+] = 0.2 M and at constant ionic strength 1.0 M (Na+, H+, Fe3+, ClO–
4). The reaction rate law is of the form: r = k
obs[CrIII], where k
obs = kQ[FeIII]/(1 + Q[FeIII]). The first-order rate constants (k), preequilibria quotients (Q) and activation parameters derived from the k values have been determined. The reaction mechanism is discussed in terms of a Lewis acid catalyzed (induced) ligand substitution. 相似文献
19.
Sergei N. Konchenko Nikolai A. Pushkarevsky Manfred Scheer 《Journal of Cluster Science》2003,14(3):299-312
The reaction of [Et4N]2[Fe3(μ 3-Q)(CO)9] (Q=Se ([Et4N]2[1b]), Te ([Et4N]2[1c])) with [Cp*M(CH3CN)3][CF3SO3]2 (M=Rh, Ir) leads to the addition of a Cp*M2+ unit to a Fe2Q face of the initial cluster. In this way four new heteronuclear clusters [MFe3(μ 4-Q)(CO)9Cp*] (M=Rh (2b, c); M=Ir (3b, c)) were obtained possessing a butterfly-shaped cluster core bridged by a μ 4-Q unit. Furthermore, reaction with the Ir starting complex leads to the metal-substituted derivatives [IrFe2(μ 3-Q)(CO)7Cp*] (4b, c) in lower yields, whose structures consist of a triangular metal core capped by a μ 3-Q ligand. The products were comprehensively characterised by spectroscopic methods and the molecular structures of 2b, 3c, and 4c were established by single crystal X-ray diffraction measurements. 相似文献
20.
S. F. A. Kettle E. Boccaleri E. Diana R. Rossetti P. L. Stanghellini M. C. Iapalucci G. Longoni 《Journal of Cluster Science》2001,12(1):175-186
When the Fe(CO)4 and M(CO)5 (M=Cr, W) groups are co-ordinated in C3v and C4v fashion, respectively, in transition metal carbonyl cluster species they contain two sets of non-symmetry related carbonyl groups. In the application of the spherical harmonic model (SHM) to the interpretation of the infrared spectra of these compounds it proves necessary first to treat these as for a normal, isolated, M(CO)4 or M(CO)5 group and then apply the SHM. This recognition gives insights into the general application of the SHM. 相似文献