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1.
《Solid State Sciences》2001,3(7):783-788
The synthesis and structural characterization of the complex [Ru(η6-C6H6)(η6-C6H4(CH3)COOCH3)] [BF4]2 (2) and of its precursor [Ru(η6-C6H4(CH3)COOCH3)Cl2]2 (1) are reported. Compound (2) has been characterized in two polymorphic modifications (2a and 2b) and the molecular organization in the solid state has been investigated. The complex [Ru(η5-C5H5)(η6-C6H5OH)][PF6] (3) has also been investigated; it has been shown to possess a disorder similar to that observed in the high temperature phase of related systems such as [Ru(η5-C5H5)(η6-C6H6)][PF6]. 相似文献
2.
《Journal of organometallic chemistry》1991,412(3):C37-C39
Single addition of the nucleophiles X− (X = H, CN, OH) to the less sterically hindered ring in [(η6-C6Me6)Ru(η6-C16H16)][BF4]2 (1) proceeds smoothly to produce, as the sole product, [(exo-η5-C6Me6X)Ru(η6-C16H16)][BF4]. Use of Na[BD4] in place of Na[BH4] gives the expected shift in ν(C-Hexo) in the infrared spectrum. 相似文献
3.
《Journal of Coordination Chemistry》2012,65(3):333-341
The reaction of [(η5-C9H7)Ru(η2-dppe)Cl] (1) with monodentate nitriles, (L) in the presence of NH4PF6 afforded the complexes [(η5-C9H7)Ru(η2-dppe)(L)]PF6, with L?=?CH3CN (2a), CH3CH=CHCN (2b), NCC6H4CN (2c), C6H5CH2CN (2d), respectively. However, reaction of 1 with NH4PF6 in methanol yielded an amine complex of the type [(η5-C9H7) Ru(η2-dppe)(NH3)]PF6 (3a). The complexes were fully characterized by spectroscopy and analytical data. The molecular structures of the complexes [(η5-C9H7)Ru(η2-dppe) (CH3CN)]PF6 (2a) and [(η5-C9H7)Ru(η2-dppe)(NH3)]PF6 (3a) have been determined by single crystal X-ray analyses. 相似文献
4.
Paul R. Raithby Jack Lewis Catherine A. Morewood M. Carmen Ramirez de Arellano Gregory P. Shields 《Journal of Cluster Science》2006,17(1):13-26
Thermolysis of [Ru3(CO)12] in cyclohexene for 24 h affords the complexes [Ru(CO)3(η4-C6H8)] (1), [Ru3H2(CO)9(μ2-η1:η2:η1-C6H8)] (2), [Ru4(CO)12(μ4-C6H8)] (3) [Ru4(CO)9(μ4-C6H8)(η6-C6H6)] (4a and 4b, two isomers) and [Ru5(CO)12(μ4-η2-C6H8)(η4-C6H8)] (5), where 1, 3, 4a and 4b have been previously characterised as products of the thermolysis of [Ru3(CO)12] with cyclohexa-1,3-diene. The molecular structures of the new clusters 2 and 5 were determined by single-crystal X-ray crystallography, showing that two conformational polymorphs of 5 exist in the solid state, differing in the orientation of the cyclohexa-1,3-diene ligand on a ruthenium vertex. 相似文献
5.
The substituted sandwich complex crystallizes in monoclinic space groupP21/m withZ=2. Twinning to the (001) direction with the special conditionc
*/4a
* = cos
* causes systematic superposition of the reciprocal lattices of both domains and results in an apparent unit cell with double volume and the reflection condition (2h)kl, l=2n. The structure solution was obtained with the subset of intensity data for the predominant individuum and converged atR = 0.040,R
w
=0.046 for 832 independent observations and 122 variables. The molecules show disorder with respect to the crystallographic mirror plane. The structure is closely related to that of decamethylruthenocene. 相似文献
6.
《Journal of organometallic chemistry》1987,333(1):61-69
Treatment of [Mo(CO)3(η-C7H7)][BF4] with either sodium amalgam or sodium naphthalide results in a reductive dimerisation to the ditropyl complex “Mo(CO)3”2(η6,η′6-C14H14). The results of an X-ray crystallographic study confirm that the hydrogen atoms of the linking carbon atoms are both endo with respect to molybdenum. The reaction of Mo(CO)6 with ditropyl, C14H14, leads to all three possible isomers of “Mo(CO)3”2(η6,η′6-C14-H14). The structure of each is assigned by its 1H NMR spectrum. 相似文献
7.
《Journal of organometallic chemistry》2005,690(24-25):6238-6246
During our low temperature NMR studies we observed two rotational isomers of the carbene complex [(η5-C5H5)(CO)2FeCH[(η6-o-MeOC6H4)Cr(CO)3]]+ (3) with the O–Me group either anti or anti to the Fp moiety. While the Cr(CO)3 group very effectively shields one face of the carbene complex from attack by the olefin, the presence of anti and anti isomers allows for the formation of both R and S configuration on C-1 of the cyclopropane through a backside or a frontside ring closure mechanism. The reaction of olefin with anti R-3 can result in R-configuration of the cyclopropane carbon C-1 through a frontside closure mechanism, or in S-configuration if backside closure takes place. In a similar manner, anti R-3 may produce S-configuration through frontside closure or R-configuration through backside closure. We previously have shown by crystallography that reaction the R-isomer of 3 with 2-methyl-propene induces predominantly a R-configuration at C-1 of the resulting cyclopropane (RR-(−)-2,2 dimethyl-1-o-methoxyphenyl(tricarbonyl chromium)cyclopropane, whereas the S-carbene results in the corresponding SS isomer. These findings are consistent with cyclopropane formation from the syn isomer through a frontside closure mechanism or from anti isomer through a backside closure mechanism. In the case of [(η5-C5H5)(CO)2FeCH[(η6-o-MeC6H4)Cr(CO)3]]+ (4), only anti isomer is observed and optical rotation data indicate that the methylcarbene exhibits the same asymmetric induction (i.e., R-carbene yields R-cyclopropane C-1 and S-carbene yields S-cyclopropane C-1) as the methoxy analogue, and the assumption of the anti isomer being the reactive one then implies that the reaction proceeds through a backside closure mechanism rather a frontside mechanism. It is very likely that this preference is also valid for the methoxy substituted complex 4. Our results on 4 indicate that the enantioselectivity of the cyclopropanation reaction is not determined by the relative abundance of the isomers. As the syn isomer is the more abundant one, the anti isomer has to be the more reactive one compared to the syn isomer. Interchange of syn and anti isomers occurs fast compared to the rate of reaction of the carbene with olefin. The fast rate of interchange of syn and anti isomers relative to the rate of reaction with olefin precludes the direct observation of any differential reactivity form a change in the syn to anti ratio in the NMR spectrum. However, the in general lower ee values observed for 3 compared with 4 are consistent with the fact that the reactive isomer is less abundant in this case. Our data thus show that enantioselectivity of cyclopropanation with “chiral at carbene” complexes is controlled by the higher reactivity of the anti isomer and occurs through a backside ring closure mechanism. 相似文献
8.
《Journal of organometallic chemistry》1989,369(3):C43-C46
One of the products of the reaction of the activated cluster Os3(CO)11(NCMe) with As(p-tol)3 in refluxing nonane has been shown by spectroscopic and X-ray crystallographic methods to be Os3(CO)9(μ3-AsC6H4CH3)(μ3-C6H3CH3), which contains a benzyne moiety bonded asymmetrically from one carbon to one osmium via a σ bond and from a second carbon to form a bridge between the remaining two osmium atoms. 相似文献
9.
《Journal of organometallic chemistry》1987,326(1):C29-C32
Reaction of the novel ruthenacyclopentatriene [(η5-C5H5)Ru(C4Ph2H2)Br] (1) with isocyanides gives the imino-2,5-diphenylcyclopentadiene complexes [(η5-C5H5Ru(η4-C5Ph2H2NR)Br] (2, R = Me, Et, Cy, t-Bu, 2,6-Me2C6H3); a novel fluxional process involving phenyl substituent rotation and imino nitrogen inversion has been identified for 2 (R = t-Bu, 2,6-Me2C6H3), the interpretation of which is supported by the X-ray crystal structure determination of 2 (R = t-Bu). 相似文献
10.
Bin Li Xing Tan Shansheng Xu Haibin Song Baiquan Wang 《Journal of organometallic chemistry》2009,694(9-10):1503-1508
Thermal reaction of Ru3(CO)12 with unsymmetrical Fv ligand 2-(tert-butylcyclopentadienyl)-indene provided [η5:η5-(tBuC5H3)(C9H6)]Ru2(CO)4 (2) in good yield. When 2 reacted with three or more equivalent of halogen X2, compounds [(η5-tBuC5H3)(C9H6X)]Ru(CO)2X (X = Br, 3; I, 4) were isolated in moderate yield. In complexes 3 and 4 only the Cp rings were coordinated with Ru(CO)2X, along with uncomplexed halogenated-indenyl rings. All the new complexes have been fully characterized. X-ray characterization of 2, 3, and 4 are also provided. 相似文献
11.
《Polyhedron》1999,18(20):2679-2685
The trinuclear oxo-capped cluster cation [(η6-C6H6)(η6-C6Me6)2Ru3(μ2-H)3(μ3-O)]+ (2) was synthesised by reacting [(η6-C6Me6)Ru(H2O)3]2+ with [(η6-C6Me6)2Ru2(μ2-H)3]+ in aqueous solution. The single-crystal X-ray structure analysis of the tetrafluoroborate salt shows the cation to contain a H2O molecule hydrogen-bonded to the μ3-oxo ligand. Acidification experiments show two protonation steps occuring at this H2O molecule and the oxo cap of the triruthenium cluster. The cluster cation 2 catalyses the hydrogenation of aromatic compounds in aqueous solution under biphasic conditions. 相似文献
12.
The electron distributions and bonding in Ru3(CO)9(
3-
2,
2,
2-C6H6) and Ru3(CO)9(
3-
2,
2,
2-C60) are examined via electronic structure calculations in order to compare the nature of ligation of benzene and buckminsterfullerene to the common Ru3(CO)9 inorganic cluster. A fragment orbital approach, which is aided by the relatively high symmetry that these molecules possess, reveals important features of the electronic structures of these two systems. Reported crystal structures show that both benzene and C60 are geometrically distorted when bound to the metal cluster fragment, and our ab initio calculations indicate that the energies of these distortions are similar. The experimental Ru–Cfullerene bond lengths are shorter than the corresponding Ru–Cbenzene distances and the Ru–Ru bond lengths are longer in the fullerene-bound cluster than for the benzene-ligated cluster. Also, the carbonyl stretching frequencies are slightly higher for Ru3(CO)9(
3-
2,
2,
2-C60) than for Ru3(CO)9(
3-
2,
2,
2-C6H6). As a whole, these observations suggest that electron density is being pulled away from the metal centers and CO ligands to form stronger Ru–Cfullerene than Ru–Cbenzene bonds. Fenske-Hall molecular orbital calculations show that an important interaction is donation of electron density in the metal–metal bonds to empty orbitals of C60 and C6H6. Bonds to the metal cluster that result from this interaction are the second highest occupied orbitals of both systems. A larger amount of density is donated to C60 than to C6H6, thus accounting for the longer metal–metal bonds in the fullerene-bound cluster. The principal metal–arene bonding modes are the same in both systems, but the more band-like electronic structure of the fullerene (i.e., the greater number density of donor and acceptor orbitals in a given energy region) as compared to C6H6 permits a greater degree of electron flow and stronger bonding between the Ru3(CO)9 and C60 fragments. Of significance to the reduction chemistry of M3(CO)9(
3-
2,
2,
2-C60) molecules, the HOMO is largely localized on the metal–carbonyl fragment and the LUMO is largely localized on the C60 portion of the molecule. The localized C60 character of the LUMO is consistent with the similarity of the first two reductions of this class of molecules to the first two reductions of free C60. The set of orbitals above the LUMO shows partial delocalization (in an antibonding sense) to the metal fragment, thus accounting for the relative ease of the third reduction of this class of molecules compared to the third reduction of free C60. 相似文献
13.
《Polyhedron》1986,5(10):1491-1497
The syntheses of the complexes [(η5-C5H5)Ru(AsPh3)(L)X] (L = PPh3 or AsPh3; X = Cl, F, Br, I, H, CN or SnCl3) and [(η5-C5H5)Ru(AsPh3)(L)(MeCN)]+Y− (Y = HgCl3, BPh4 or Zn2Cl6) are described. They were characterized by elemental analyses, IR, UV and visible, PMR spectroscopy, X-ray powder diffraction, and mass spectral studies. 相似文献
14.
《Comptes Rendus de l''Academie des Sciences Series IIB Mechanics Physics Astronomy》1999,2(4):205-208
The reactions of [MCp*(η6-C6Me6)][PF6], M = Fe: 1, Ru: 2, Cp* = η5-C5Me5, with KOH (in DME) or tert-BuOK (in THF) and methyl iodide, allyl bromide or benzyl bromide are regioselective on the arene ligand only for 2, giving the complexes [RuCp*{η6-C6(CH2R)6}][PF6], R = methyl (3), allyl (4) or benzyl (5), although some formations of C-C bonds also occur on the Cp* ligand in the case of the reactions of allyl and benzyl bromides. This contrasts with the complete lack of regioselectivity formerly observed with the iron analogue 1, and is best taken into account by the difference of steric effects which are less marked in 2 than in 1. 相似文献
15.
《Journal of organometallic chemistry》1988,354(3):C33-C36
Reaction of (η5-C5Me5)Re(NO)(PPh3)(CH3) and HBF4 · OEt2 in CH2Cl2 at −78°C gives the dichloromethane complex [η5-C5Me5Re(NO)(PPh3)(ClCH2Cl)]+ BF4−, which undergoes the title transformation at −35°C. The ReClCH2Cl carbon is attacked by halide nucleophiles (X−) to give XCH2Cl and the chloride complex (η5-C5Me5)Re(NO)(PPh3)(Cl), and exhibits a 13C NMR resonance that is coupled to phosphorus (d, 3J(CP) 5.0 Hz) and geminal hydrogens (t, 1J(CH) 186 Hz). 相似文献
16.
S. P. Khranenko E. A. Bykova K. V. Yusenko A. P. Tyutyunnik S. A. Gromilov 《Journal of Structural Chemistry》2013,54(5):931-936
X-ray crystallographic analysis is used to determine the crystal structures of [Ru(NH3)6](MoO4)Cl·3H2O and [M(NH3)6](ReO4)3·2H2O (M = Ru, Ir) complex salts. The features of the fragment packing are studied. 相似文献
17.
《Polyhedron》1986,5(6):1217-1221
The preparation, and electronic, 1H and 13C NMR spectra of the complex ions [Ru(η6-C6H6)L3]2+ (L = acetonitrile, dimethylsulphoxide, dimethylsulphide or tetrahydrothiophene) from [Ru(η6-C6H6)(H2O)3]2+ are reported. The NMR data of coordinated benzene are discussed in terms of the π-backbonding capacity of the monodentate ligand. 相似文献
18.
《Journal of organometallic chemistry》1987,330(3):415-428
The crystal and molecular structures of (η5-C5H5)Fe[η5--C5H4CCo3(CO)9] (1), Pna21, α 17.354, b 11.463, c 11.207 Å Z = 4, R = 0.053, Rw = 0.056 for 939 reflections (I>3σ(I)) at 293 K, and (η5-C5H5Fe[η5--C5H4CCo3(η5C5H5)3CH] (2), P21/n, a 13.807(9), b 11.254(4), c 13.991(9) Å, β 99.98(5)°, Z = 4, R = 0.033 and Rw = 0.033 for 3051 observed reflections (I>3σ(I)) at 180 K, have been determined by X-ray methods.The results provide a detailed characterisation of related tricobalt-carbon complexes directly bound to ferrocene residues. In 1 the ferrocenyl moiety tops the pyramidal CCo3 cluster core, while in 2 the CCo3C core is bipyramidal with a ferrocenyl substituent on one capping carbon atom and a hydrogen atom at the other. In both cases the ferrocenyl group is tilted towards one cobalt atom of the cluster core, a distortion believed to be the consequence of the non-degeneracy of the carbyne p(π) orbitals resulting from a cooperative π-interaction between the clusters and the ferrocenyl substituents. 相似文献
19.
20.
《Journal of organometallic chemistry》1987,323(3):371-384
The reactions of mononuclear carbene complexes of W and Fe of the type CO)mMC(OR)(CH2nCHCR′″ (M = FE, W; m = 4 and 5; n = 0, 2, 3; R′, R″ = C, CH3, OEt) with Fe(CO)5 have been studied. In all cases the reaction leads to new hetero (WFe) or homo (FeFe) μ-alkylidene complexes, the position of the double bond depending strongly on n. 相似文献