Category: 1271-19-8

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Titanocene and zirconocene complexes containing dendrimer-substituted cyclopentadienyl ligands – Synthesis and ethylene polymerization

This paper describes the synthesis of a series of titanium and zirconium metallocenes bearing one or two first-generation silane dendritic wedges as bulky substituents at their cyclopentadienyl rings. Wedges (R2R?SiCH2CH2)3SiCl [R = R? = Et (1); R = Ph, R? = Me (2)] were prepared by hydrosilylation of chlorotrivinylsilane with R2R?SiH. They were reacted with K(C5H5 and, subsequently, with KH to give K[(R2R?SiCH2 CH2)3Si(C5H4)] [R = R? = Et (3); R = Ph, R? = Me (4)]. The dendronized cyclopentadienides 3 and 4 were the starting materials for preparation of the mixed-ring titanocenes [{(R2R?SiCH2 CH2)3SiC5H4} (C5R?5)TiCl2] [R = R? = Et, R? = H (5), R? = Me (6); R = Ph, R? = Me, R? = H (7), R? = Me (8)] or the symmetrically substituted metallocenes [{(Ph2MeSiCH2 CH2)3SiC5 H4}2MCl2] [M = Ti (9), Zr (10)]. Cyclic voltammograms and catalytic behavior of all the new metallocenes in ethylene polymerization, using MAO as a co-catalyst, have been studied and compared to that of related non-dendritic complexes. Polyethylene polydispersities increase with the number of dendritic wedges in the catalyst, while activities decrease. Bimodal molecular weight distributions were clearly observed for the bis-dendritic titanocene 9. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 1271-19-8, name is Titanocenedichloride, introducing its new discovery. Computed Properties of C10Cl2Ti

Evolved gas analysis of Ti(C5H5)2Cl 2 by means of Li+ ion attachment mass spectrometry

Characterization of the compound Ti(C5H5) 2Cl2 was studied using Li+ ion attachment mass spectrometry (IAMS) as an analytical methodology. Since this target compound is used as an anticancer drug in the treatment of leukemia, accurate and rapid monitoring methods for the determination of titanium drugs in a hospital environment are desirable. A quadrupole mass spectrometry system along with a Li+ ion attachment technique and a direct inlet probe (DIP) produced the Li+ adduct of Ti(C5H5)2Cl 2, Ti(C5H5)2Cl2Li +. The DIP also was used to study the temperature-resolved behavior of this compound. The slope of the plot of signal intensity of Ti(C 5H5)2Cl2Li+ versus temperature for Ti(C5H5)2Cl2 sublimation from 60 to 100 C was used to determine an apparent activation energy (Ea) of 124.43 kJ/mol for the sublimation of Ti(C 5H5)2Cl2. This value is comparable to the reported value of 118.8 kJ/mol for molar enthalpy of sublimation of Ti(C5H5)2Cl2. These results demonstrate that the IAMS methodology can be used to study the enthalpy of sublimation for d-metal complex materials.

The proportionality constant is the rate constant for the particular unimolecular reaction. the reaction rate is directly proportional to the concentration of the reactant. I hope my blog about 1271-19-8 is helpful to your research. Computed Properties of C10Cl2Ti

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 1271-19-8, name is Titanocenedichloride, introducing its new discovery. Quality Control of: Titanocenedichloride

Dramatic rate acceleration in titanocene catalyzed epoxide openings: Cofactors and Lewis acid cocatalysis

High synthetic efficiency concerning yield and catalytic turn-over in intermolecular C-C bond forming reactions of radicals derived from epoxides can be achieved by means of hydrogen bonding with cofactors or by Lewis acid cocatalysis.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

Chemistry is traditionally divided into organic and inorganic chemistry. Computed Properties of C10Cl2Ti. The former is the study of compounds containing at least one carbon-hydrogen bonds.In a patent£¬Which mentioned a new discovery about 1271-19-8

Synthesis and structure of 1-metallacyclopent-3-yne complexes of group 4 metals

Five-membered metallacyclic alkyne complexes of titanium and hafnium, 1,1-bis(cyclopentadienyl)-1-titanacyclopent-3-yne (2) and trans-1,1- bis(cyclopentadienyl)-2,5-trimethylsilyl-1-hafnacyclopent-3-yne (6), were synthesized and structurally characterized. The structural analysis of titanium complex 2 implied a larger contribution of an eta4-pi,pi- coordinated structure. The hafnium compound 6 has a similar structure to the corresponding zirconium analogue (1a), although slight differences in the bond lengths and angles were observed. A novel 1-zirconacyclopent-3-yne complex, 1,1-bis(methylcyclopentadienyl)-2,5-bis(trimethylsilyl)-1-zirconacyclopent-3- yne (5), was also prepared and the structure of the trans-isomer was determined.

Note that a catalyst decreases the activation energy for both the forward and the reverse reactions and hence accelerates both the forward and the reverse reactions.Computed Properties of C10Cl2Ti, you can also check out more blogs about1271-19-8

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

Electric Literature of 1271-19-8, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.1271-19-8, Name is Titanocenedichloride, molecular formula is C10Cl2Ti. In a article£¬once mentioned of 1271-19-8

Synthesis and characterization of Cp2Ti-containing organometallics via in situ oxidative-addition of ‘Cp2Ti’ intermediate

A simple and convenient route for synthesizing Cp2 Ti-containing compounds (RS)2TiCp2 (1, R = 1-C10H7; 2, R = CH2=CHCH2; 3, R = n-C5H11; 4, R = CH2CO 2Me; 5, R = CH2CO2Et; 6, R = (eta5-C5H5)Fe(eta5 -C5H4CH2)) and [eta2-OC(Ph) =C(Ph)O] TiCp2 (7) has been developed. This route starts from Cp2TiCl2 and involves an in situ oxidative-addition of the intermediate ‘titanocene’ with corresponding RSSR and benzil. While 7 was previously prepared by another route, 1-6 and one starting material [(eta5-C5H5) Fe(eta5-C5H4CH2)] 2S2 (8) are new and have been characterized by elemental analysis, IR and 1H-NMR spectroscopy, as well as by X-ray diffraction analysis for 1, 6 and 7. Furthermore, the electrochemical properties of 1-6 have been studied by cyclic voltammetry.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 1271-19-8, molcular formula is C10Cl2Ti, introducing its new discovery. Application In Synthesis of Titanocenedichloride

Tunable titanocene lewis acid catalysts for selective friedel-crafts reaction of indoles and N-sulfonylaldimines

A newc strategy to control the selective Friedel-Crafts reaction of indoles and imines under mild conditions was developed. Phenol derivatives were established as efficient ligands to finely tune the activity of titanocene dichloride. Cp2TiCl2 and phenol catalyzed the mono-Friedel-Crafts reaction of indoles and N-sulfonyl aldimines with good yields (91 %), whereas o-aminophenol significantly enhanced the activity of the titanocene catalyst and promoted the synthesis of bisindole with excellent yields (98 %). The new organometallic Lewis acid catalysts are air-tolerant, can be used with low catalyst loading (3 mmol-%) and are compatible with -NO2, -F, -Cl, -Br, and -OMe (30 examples with yields from good to excellent). The titanocene catalysts were fully characterized by NMR and HRMS analysis. The results suggest that Cp2TiCl(OC6H5) (I) and Cp2TiCl(OC6H4NH3+Cl-) (II) were catalytic species for the mono- and double-Friedel-Crafts reactions, respectively. Distinguished from single functional acid catalysts I, catalyst II showed a catalytic cooperative effect of two acid components, which led to a fine tuning of the reactivity as well as to the selectivity of the desired reaction pathways. A Ti-catalyzed, highly selective Friedel-Crafts reaction of indoles and imines has been developed. Cp2TiCl2 and phenol, with a single Lewis acid site, catalyzed the mono-Friedel-Crafts reaction of indoles and N-sulfonylaldimines, whereas o-aminophenol enhanced the acidity of titancene catalyst, enabling both Lewis and Bronsted acid sites to promote the synthesis of bisindole.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Effects of methyl substituents at the cyclopentadienyl ligand on the properties of C2H5TiCl3 and C5H5TiAl2CL8-x(C2H5)x (x = 0-4) complexes

The methyl substituents in the series of <*>pTiCl3 compounds (<*>p = Cp, MeCp, Me3Cp, Me4Cp, Me5Cp and EtMe4Cp) shift the position of their CT absorption band from lambda = 384 nm to max. 438 nm and decrease the rate of reduction of <*>pTiCl3 by ethylaluminium compounds yielding the trinuclear <*>pTiAl2Cl8-xEtx (x = 0-4) complexes.In the <*>pTiCl3/excess Et2AlCl systems the rate of reduction was controlled by pseudomonomolecular decomposition of the proposed octahedral intermediate <*>pTiEt(Cl2AlEt2)(Cl3AlEt).The rate constants for reduction decreased in the above series of <*>pTiCl3 compounds from 1.10*10-3 to 6.15*10-5 s-1.The methyl substituents in the <*>pTiAl2Cl8-xEtx complexes shifted the charge transfer bands to longer wavelengths, the d-d transition to shorter wavelengths and the ESR g-value away from the free electron value.The opposite shifts were induced by the replacement of the outer chlorine atoms in the chloroaluminate ligands by ethyl groups.On going from Cp to Me5Cp the thermal stability of the <*>pTiAl2Cl8 complexes decreased while the complexes <*>pTiAl2Cl4Al4 became stable even with the excess of Et3Al.The <*>pTiAl2Cl8-xEtx complexes were also formed in the redox reaction of non-dimerizing methylcyclopentadienes (Me3CpH/EtMe4CpH) with bis(di-mu-chloroalane)(benzene)titanium(II) complexes C6H6*TiAl2Cl8-xEtx (x = 0-2).The reaction was found stoichiometric except for the perchloro complexes forming diamagnetic byproducts.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

Electric Literature of 1271-19-8, In heterogeneous catalysis, the catalyst is in a different phase from the reactants. At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 1271-19-8, name is Titanocenedichloride. In an article£¬Which mentioned a new discovery about 1271-19-8

DINUCLEAR TITANOCENE CHALCOGENIDES AS SULFUR AND SELENIUM TRANSFER REAGENTS IN RING SYNTHESIS

The dinuclear titanocene complexes Cp4Ti2S6, Cp4Ti2S4 and Cp4Ti2Se4 have been reacted with SCl2, S2Cl2, and Se2Cl2, respectively.The reaction products are rings of type Sn (n=6…20) and six-, seven- and eight-membered rings of type SexSy, respectively, which have been characterized by HPLC, Raman and Se-NMR spectroscopy, as well as X-ray diffraction on single crystals.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

Electric Literature of 1271-19-8, The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.1271-19-8, Name is Titanocenedichloride, molecular formula is C10Cl2Ti. In a Article£¬once mentioned of 1271-19-8

Coordination Chemistry of the Tris(pentafluoroethyl)stannate(II) Anion, [Sn(C2F5)3]?

In this contribution the syntheses of transition metal complexes of the electron-withdrawing Sn(C2F5)3 ligand are presented. The reaction of HSn(C2F5)3 with organometallics LnM?R (M = Zn, W, Mo; R = Et, Me; L = CO, Cp), metal carbonyls [Ni(CO)4], and [{Fe(CO)2Cp}2], as well as chloro complexes such as [TiCl2Cp2], furnished the corresponding stannylated compounds. The electron-deficient Sn(C2F5)3 ligand significantly influences the IR spectroscopic and structural features with respect to related non-fluorinated stannyl complexes.

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Metal catalyst and ligand design,
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Titanocene catalyzed 4-exo cyclizations: Mechanism, experiment, catalyst design

A method for the preparation of a variety of cyclobutanes via 4-exo cyclization of radicals is presented. Radical generation is carried out by electron transfer from titanocene(III) chlorides to epoxides. The reaction relies on the acceleration of the cyclization through the use of alpha,beta-unsaturated carbonyl compounds as radical traps and the thermodynamic stabilization of the cyclobutylcarbinyl radicals through conjugation. The mechanism of the transformation was investigated by a combined theoretical and experimental study. The computational results provide the crucial energetic and structural features of pertinent intermediates and transition structures. Moreover, the origins of the diastereoselectivity of the 4-exo cyclization are outlined for the first time. Catalysts for those cases where “Cp2TiCl” did not perform in a satisfactory manner have been devised. Through the introduction of tert-butyl or cyclo-hexyl substituted cyclopentadienyl ligands the longevity of the pivotal beta-titanoxy radicals is increased sufficiently enough to enable the slow but often surprisingly diastereoselective formation of the cyclobutylcarbinyl radical. The resulting transformation constitutes the first general approach to cyclobutanes using radical chemistry.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI