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Bis(trimethylphosphane)titanocene (1) and (eta2-Ethene)(trimethylphosphane)titanocene (2) react with one equivalent of allene (3a), phenylallene (3b), 1,1-dimethylallene (3c), and 1,1-diphenylallene (3d) readily by displacement of one trimethylphosphane from 1 and of ethene from 2 to give regiospecifically the corresponding (eta2-allene)(trimethylphosphane)titanocene complexes 4a-d in good yields.From (eta2-1-butene)(trimethylphosphane)zirconocene (6) and 3d the corresponding (1,2-eta2-3,3-diphenylallene)zirconocene complex 7d is obtained in the same manner.The structures of these new allene complexes have been established unambiguously by 1H- and 13C-NMR-spectroscopy.A crystal structure analysis of the titanocene complex 4d confirms the spectroscopic structure determination.All the above mentioned allene-metallocene complexes consume readily a second equivalent of the allene derivatives to produce, in most cases, regiospecifically the corresponding 1-metalla-2,5-dimethylenecyclopentane derivatives 5a-d (M = Ti) and 8c, d (M = Zr); only the (allene)zirconocene complex 7a gives rise to a 1:1 mixture of the regioisomers 8a and 9.More conveniently 5a-d and 8c, d are synthesized directly from metallocene dichloride and the corresponding allenes 3. – Key Words: Titanocene, complexes of / Zirconocene, complexes of / Allene complexes / 1-Metalla-2,5-dimethylenecyclopentane complexes

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

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The bisthionylimide complex (Cp=eta5-C5H5) was prepared by reaction of and KNSO and its X-ray crystal structure determined; reaction of this compound with LiN(SiMe3)2 yielded .

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Reference:
Metal catalyst and ligand design,
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The CpTiCl2. radical photogenerated from Cp2TiCl2 has been found to add oxidatively to various ortho- and para-quinones to give titanium(IV) complexes of semiquinone radical-anionic ligands, which have been characterized by ESR spectroscopy.Detailed investigation of the reaction with 3,5-di-t-butyl-1,2-benzoquinone reveals that o-quinones add to the titanium(III) atom primarily through one oxygen atom only, the chelate ring being formed in a subsequent intramolecular displacement of a weakly bound solvent molecule (toluene, tetrahydrofuran, pyridine).Information was obtained on the redox and coordination properties of CpTiCl2. and its oxidaton product.The reactant orbital matching leading to the oxidative addition is briefly discussed.

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

Brief introduction of Titanocenedichloride

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The syntheses of 32 complexes of the type (eta-C5H5)2Ti(OOCC6H4X)2 are reported together with their mass, 1H NMR, 13C NMR, mid- and far-IR spectra.The data are consistent with a model in which the Ti-OOC bond strength (weaker than that of Ti-Cp and Ti-Hal) is stabilized by electron-withdrawing substituents X on the phenyl rings.The electronic influence of X also extends into the cyclopentadienyl rings.

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

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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. Quality Control of: Titanocenedichloride

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An asymmetric total synthesis of ent-pyripyropene A was achieved by a convergent synthetic route. We used our originally developed TiIII-catalyzed radical cyclization to construct an AB-ring portion that consisted of a trans-decalin skeleton with five contiguous stereogenic centers. The coupling between the AB-ring and the DE-ring portions, and a subsequent C-ring cyclization, led to the total synthesis of ent-pyripyropene A. An evaluation of the insecticidal activity of ent-pyripyropene A against two aphid species revealed that ent-pyripyropene A was 35-175 times less active than naturally occurring pyripyropene A. This result indicated that the biological target of pyripyropene A recognizes the absolute configuration of pyripyropene A. Radical chemistry! An asymmetric total synthesis of ent-pyripyropene A (see scheme) was achieved by a convergent synthetic route. Stereoselective synthesis of the AB-ring was achieved by the originally developed TiIII-catalyzed radical cyclization. An evaluation of insecticidal activity of ent-pyripyropene A against two aphid species revealed that ent-pyripyropene A was 35-175 times less active than naturally occurring pyripyropene A.

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

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Reaction of Cp2Ti[eta2-(CSiMe3) 2] with an alpha-aryloxy ketone produces a Ti(IV) enolate aryloxide complex. Selective protonolysis of the enolate ligand or both Ti-OR bonds can be achieved with various acids. The reaction of the enolate aryloxide with 1-phenyl-2-phenoxyethanol is catalyzed by a mixture of NEt3 and [HNEt3]X (X = OTf, BPh4).

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

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New polynuclear complexes, (L1)3 M2{M 2 = Cr(III) (4a, 4b), Fe(III) (5), Co(III) (8)}, (L1) 2M2(L2)2 {M2 = Co(II)(7), Ni(II) (9)}, (L1)2M2(O)L2 {M 2 = V(IV) (6)} and L1M2Cp2 {M 2 = Ti(III) (10)} with L1 = (CO)M1=C{C=NC(CH 3)=CHS}O (M1 = Cr or W) and L2 = 4-methylthiazole or THF, are described. The molecular structures of these complexes determined by X-ray diffraction show that the Fischer-type carbene complexes act as bidentate ligands towards the second metal centre, coordinating through C(carbene)-attached O-atoms and imine N-atoms of the thiazolyl groups to form five-membered chelates with the oxygen atoms in the mer configuration. Isostructural complexes have similar characteristic band patterns in their far-IR spectra. Cyclic voltammetry of selected complexes reveals the oxidation of the carbene complex ligand between 1.01 and 1.29 V. Oxidation of the central metal (M2) takes place at 0.56 and 0.86 V for 7 and 9, respectively. Three stepwise reductions of Cr(III) to Cr(0) occur for 4a and 4b in the region -0.51 to -1.58 V. These new ligand types and other variants thereof should find application in ligand design with the first metal – and other ligands attached thereto – in the carbene complex ligand, playing an important role.

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

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A simple new route to access heterometallic alkoxo precursors for a wide range of materials is reported. This unique synthetic method comprises elimination of the cyclopentadienyl ring from Cp2MCl2 (M = Ti, Zr) as CpH in the presence of M?(OR)2 (M? = Ca, Mn; OR = OCH2CH2OCH3 or OEt) in an alcohol as a source of protons. In one-pot reactions, we have prepared four different compounds with Ti2Ca4(mu6-O), Cp 2Zr2Ca4(mu4-Cl), Zr 10Mn10(mu3-O)14, and Cp 3Ti2(mu-OEt)2 motifs. The compounds were characterized by single-crystal X-ray structural analysis and NMR spectroscopy.

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

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The reaktion of the metallocene dichlorides Cp2MCl2 (Cp = eta5-C5H5; M = Ti, Zr, Hf, Mo, W) and Cp’2TiCl2 (Cp’ = eta5-C5H4CH3) with equimolar amounts of dilithium-benzene-o-diselenolate, 1,2-(LiSe)2C6H4, gives the chelate complexes Cp2M(Se2C6H4)(M = Ti(I), Zr(II), Hf(III), Mo(IV), W(V) and Cp’2Ti(Se2C6H4) (VI).CpTiCl3 reacts with 1,2-(LiSe)2C6H4 to give CpTiCl(Se2C6H4) (VII).The ring inversion activation parameters for I-VI can be determined by means of temperature-dependent 1H NMR spectroscopy in solution.The fragmentation behaviour of I-VII in the mass spectrometer has been investigated by pursuing metastable transitions, using linked-scan techniques.

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

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Hydrosilylation of olefins catalyzed by Cp2TiCl2/Sm (Cp = cyclopentadienyl) under solvent free conditions have been investigated. By using Cp2TiCl2/Sm as catalyst system, beta-adducts and hydrogenation products were detected. Hydrosilylation of olefins catalyzed by Cp2TiCl2/LiAlH4 under room temperature has also been studied. The influence of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) on Cp2TiCl2/Sm and Cp2TiCl2/LiAlH4, respectively, indicated that hydrosilylation of olefins catalyzed with Cp2TiCl2/Sm went through a free radical reaction pathway while a coordination mechanism was applied for Cp2TiCl2/LiAlH4 catalyst system.

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