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Reaction of metallocenes with maleic anhydride

Spectral investigation applying UV, IR, and 1H NMR techniques to the reaction of ferrocene, titano- and zirconocene dichlorides with maleic anhydride was carried out. It was found that in all cases charge transfer complexes were formed. It was showed that the structure of the metallocene affected both the process of the formation and structure of the complexes.

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

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Titanium complexes of dialkanolamine ligands: Synthesis and structure

Synthesis of the title compounds, viz. [RN(CH2CH 2O)-(CHR1CR2R3O)]Ti(OiPr) 2 (13-15) and [RN(CH2CH2O)-(CHR 1CR2R3O)]2Ti (18-28), by the reaction of one or two equivalents of the corresponding dialkanolamines RN(CH2CH2OH)(CHR1CR2R3OH) (1-12) with Ti(OiPr)4 is reported. Other routes to [RN(CH 2CH2O)(CHR1CR2R3O)] 2Ti, such as the reaction of Ti(CH2Ph)4 with dialkanolamine and the reaction of TiCl4(THF)2 with dialkanolamine/Et3N were also tested. Dimeric titanocane 16, [PhCH2N(CH2CH2O)2Ti(OMe) 2]2, was obtained from the reaction of one equivalent of dialkanolamine 3 with CpTi(OMe)3. PhCH2N(CH 2CH2O)2-Ti(OMenth)2 (17) was prepared from the transalkoxylation reaction of 15 with two equivalents of menthol. The composition and structures of all novel compounds were established by 1H and 13C NMR spectroscopy as well as elemental analysis data. The possible solution structure features of 13-28 are discussed. The single-crystal X-ray diffraction study of titanocane 16 clearly indicates a dimeric structure for this compound in the solid state. According to X-ray data, compounds [PhCH2N(CH2CH2O)2] 2Ti (19), [MeN(CH2CH2O)-(CH2CHPhO)] 2Ti (20), [MeN(CH2CH2O)(CH2CPh 2O)]2Ti (23), erythro-[MeN(CH2CH 2O)(CHPhCHPhO)]2Ti (24), threo-[MeN(CH2CH 2O)(CHPhCHPhO)]2Ti (25), and {MeN(CH2CH 2O)[CH(CH2)4CHO]}2Ti (27) possess a monomeric structure with a hexacoordinate titanium atom in the solid state. Among them complexes 19, 20, 23, 25, and 27 are characterized by a cis disposition of the nitrogen atoms in the coordination environment of the Ti atom, while nitrogen atoms in 24 occupy trans positions. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

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Metal catalyst and ligand design,
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Study of the anticancer properties of methyl- and phenyl-substituted carbon- and silicon-bridged ansa-titanocene complexes

The previously known complexes [Ti{(Me2CMe2C) (eta5-C5H4)2}Cl2] (1), [Ti{Me2C(eta5-C5H4) 2}Cl2] (2), [Ti {Me2Si(eta5-C 5H4)2}Cl2] (4), [Ti{MePhSi(eta 5-C5H4)2}Cl2] (5) and [Ti{MePhSi(eta5-C5Me4)2}Cl 2] (6) have been prepared following reported procedures. The novel complex [Ti{MePhC(eta5-C5H4) 2}Cl2] (3) has been prepared and characterized. The cytotoxic activity of 1-6 has been tested after 72 h on melanoma A375 and B16, prostate cancer DU145 and LNCaP and colon cancer HCT116, SW620 and CT26CL25 cell lines observing a high cytotoxic activity of complexes 1 and 6 compared to the reference compound ([Ti(eta5-C5H5) 2}Cl2]). 1 and 6 have also been tested against primary normal mouse keratinocytes and lung fibroblasts. While viability of both type of primary cells was significantly less affected by 1 in comparison to the reference compound [Ti(eta5-C5H5) 2Cl2], compound 6 was completely nontoxic for nonmalignant cells, indicating a potential selectivity of this compound towards cancer cell lines. In addition CFSE staining, cell cycle analysis, AnnexinV-FITC/PI staining, detection of caspase activity and mitochondrial potential showed that 1 and 6 were acting through inhibition of proliferation and subsequent induction of mitochondrial dependent apoptosis in colon cancer cell lines, HCT116 and SW620, which express low sensitivity to cisplatin. Compound 6 was found to be the leading drug in this group since it shows the fastest and most selective anticancer profile.

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

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Organometallic titanocene-gold compounds as potential chemotherapeutics in renal cancer. Study of their protein kinase inhibitory properties

Early-late transition metal TiAu2 compounds [(eta-C5H5)2Ti{OC(O)CH2PPh2AuCl}2] (3) and new [(eta-C5H5)2Ti{OC(O)-4-C6H4PPh2AuCl}2] (5) were evaluated as potential anticancer agents in vitro against renal and prostate cancer cell lines. The compounds were significantly more effective than monometallic titanocene dichloride and gold(I) [{HOC(O)RPPh2}AuCl] (R = -CH2- 6, -4-C6H4- 7) derivatives in renal cancer cell lines, indicating a synergistic effect of the resulting heterometallic species. The activity on renal cancer cell lines (for 5 in the nanomolar range) was considerably higher than that of cisplatin and highly active titanocene Y. Initial mechanistic studies in Caki-1 cells in vitro coupled with studies of their inhibitory properties on a panel of 35 kinases of oncological interest indicate that these compounds inhibit protein kinases of the AKT and MAPKAPK families with a higher selectivity toward MAPKAPK3 (IC50 3 = 91 nM, IC50 5 = 117 nM). The selectivity of the compounds in vitro against renal cancer cell lines when compared to a nontumorigenic human embryonic kidney cell line (HEK-293T) and the favorable preliminary toxicity profile on C57black6 mice indicate that these compounds (especially 5) are excellent candidates for further development as potential renal cancer chemotherapeutics.

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Metal catalyst and ligand design,
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Electronic and Steric Design of Novel Group 13 Lewis Acids and Their Synthesis via Metal-Tin Exchange Reactions (1): Toward the Ideal Olefin Polymerization Catalyst

Group 13 Lewis acids have long played a leading role as catalysts in organic synthesis, extending from the discovery of AlCl3-catalysis by Friedel and Crafts in 1877 through the Aufbau-synthesis of unsolvated aluminum alkyls from ethylene by Ziegler in 1952 and culminating in the discovery of poly(methylaluminoxane) (MAO) cocatalysis of olefin polymerization by Sinn and Kaminsky in 1976. In our current work we present how electronic and steric contributions of the ligands attached to the particular Group 13 metal can modulate the resultant Lewis acidity. The inherent Lewis acidity of the Group 13 metal center itself is further dependent upon the extent that its available npz-orbital might interact with adjacent unshared or pi-electrons of the ligand system. In order to evaluate the effect of such electronic factors on their Lewis acidity, both a series of bidentate Group 13 organoboron and organoaluminum candidate acids, as well as their antiaromatic metallole analogs, have been synthesized by exchange reactions between the corresponding organotin compound and the appropriate metal halide. Their Lewis acidity has been evaluated based upon their efficacy as a cocatalyst with titanocene(IV) methyl chloride or titanocene(IV) dichloride in effecting the polymerization of ethylene.

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

Discovery of Titanocenedichloride

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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. Safety of Titanocenedichloride

Preparation of Thionylimide Complexes of Titanium, Zirconium, and Hafnium. Crystal Structure of

The compounds , (Zr(cp)(eta-C5Me5)2(NSO)2>, , and (Hf(cp)(eta-C5Me5)(NSO)2> (cp = eta-C5H5) have been prepared from corresponding metal halides and K(NSO).The transition-metal-bonded NSO groups can be transformed into NSNSiMe3 by reaction with Li, giving .A compound containing three NSO ligands has been prepared from the reaction of SnMe3(NSO) and .The X-ray crystal structure of reveals a pseudo-tetrahedral co-ordination of the metal, with two nitrogen-bonded NSO ligands forming a nearly planar Zr(NSO)2 unit.

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

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Preparation of titanium molecular species supported on mesostructured silica by different grafting methods

Titanium supported on SBA-15 mesoporous silica has been synthesised containing different titanium loading prepared by chemical grafting using titanocene dichloride as precursor and over different treated silica surfaces. A comparative study using MCM-41 mesoporous silica as support is also reported. The type of silica support and its surface properties as well as the initial concentration of Ti precursor in the organic solution influences clearly the incorporation of Ti species. The materials after grafting treatment were characterised by different conventional techniques including XRD, FT-IR, DR UV-Vis and nitrogen adsorption. The titanium containing SBA-15 silica shows hexagonal mesoscopic order and pore sizes up to 70 A with surface areas up to 600 m2/g and titanium content ranging from 1 to 3 wt.%. DR UV-Vis of Ti containing SBA-15 silica after removal of the organic ligand shows the presence of Ti isolated species tetrahedrally coordinated and the absence of bulky TiO2 phases. Likewise, these materials upon calcination were catalytically active for the epoxidation of styrene with TBHP exhibiting a significant selectivity towards the epoxide with negligible leaching of Ti species.

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

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Cuprate addition to a 6-substituted pentafulvene – Preparation of sec-alkyl-substituted titanocene dichlorides and their biological activity

The copper-catalysed (10 mol-% CuBr¡¤SMe2, CuCN¡¤LiCl or CuI/PPh3) addition of RMgBr to the pentafulvene 1-(cyclopenta-2,4-dien-1-ylidenemethyl)-2-methoxybenzene allows the formation of cyclopentadienyl derivatives with alpha-CHR(2-MeOPh) sidechains (R = Me, Et, nBu, iBu, allyl, Ph) without H- transfer. The deprotonation of these sec-alkyl-substituted cyclopentadienyls followed by the addition of TiCl 4 allows the isolation of TiCl2{eta5-C 5H4CHR(2-OMePh)} as rac/meso mixtures that show activity against human colon, breast and pancreatic cell lines (GI50 2.3-42.4 muM). The direct addition of alkyllithium and Grignard reagents with beta-hydrogen atoms to fulvenes has been dogged with the problem of competing hydride transfer. Copper catalysis overcomes this and allows access to titanocene dichlorides with high anticancer activity. Copyright

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

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Solid-state chlorine nmr of group iv transition metal organometallic complexes

Static solid-state 35 Cl (I ) 3/2 ) NMR spectra of the organometallic compounds Cp 2 TiCl 2 , CpTiCl 23 , Cp 2 ZrCl 2 , Cp 2 HfCl 2 ,Cp* 2 ZrCl 2 , CpZrCl 3 , Cp*ZrCl 3, Cp 2 ZrMeCl, (Cp 2 ZrCl) 2 mu-O, and Cp 2 ZrHCl (Schwartz’s reagent) have been acquired at 9.4 T withthe quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) sequence in a piecewi se manner. Spectra of several samples have also been acquired at 21.1 T.The electric field gradient (EFG) tensor parameters, the quadrupolar co upling constant (C Q ) and quadrupolar asymmetry parameter (Q), are readily extracted from analytical simulations of the spectra. The 35Cl EFG and chemicalshift tensor parameters are demonstrated to be sensitive probes of metallocene structure and allow for differentiation of monomeric and oligomeric structures. First-principles calculations of the35Cl EFG parameters successfully reproduce the experimental values and trends. The origin of the observed values of C Q (35Cl) are f urther examined with natural localized molecular orbital (NLMO) analyses. The combination of experimental and theoretical methods applied to themodel compounds are employed to structurally characterize Schwartz’s re agent (Cp 2 ZrHCl), for which a crystal structure is unavailable. Aside from a fewselect examples of single-crystal NMR spectra, this is the first reported application of solid-state 35Cl NMR spectroscopy tomolecules with covalently bound chlorine atoms. It is anticipated that the methodology outlined herein will find application in the structural characterization of a wide variety of chlorine-containing transition-met al and main-group systems.

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Metal catalyst and ligand design,
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Living organotitanium(IV)-catalyzed polymerizations of isocyanates

An organotitanium(IV) compound, TiCl3OCH2CF3, 1, was found to polymerize n-hexyl isocyanate to high yields and without the formation of cyclic trimer. CpTiCl2L (L = -OCH2CF3, -N(CH3)2, -CH3), 2-4, respectively, likewise polymerized n-hexyl isocyanate but also polymerized isocyanates in the presence of donor solvents and isocyanates possessing donor functional groups, activated olefins, and strained olefins. The activity of the organotitanium(IV) catalysts decreased with increasing steric bulk about the metal center and increasing electron donation to the metal center from the ligands. The polymerization of n-hexyl isocyanate using organotitanium(IV) compounds is living. The PDIs of PHIC synthesized using catalysts 1-4 were found to range from 1.05 to 1.2. The molecular weight of the polymer formed in polymerizations of n-hexyl isocyanate using catalysts 1-4 varied linearly as a function of the monomer-to-initiator ratio and the percent conversion of the polymerization. Polymerizations using 2 can be endcapped quantitatively, and well-defined block copolymers can be synthesized using catalysts 1-4. The kinetics for polymerizations using catalysts 1 and 2 are first-order in both monomer and catalyst (k1 = 8.5 x 10-4 mol L-1 s-1, k-1 = 3.8 x 10-4 s-1). The active endgroup of a polymerization using 3 was observed using IR spectroscopy, and the frequency of the IR stretch (1548 cm-1) was consistent with an eta2-amidate endgroup structure. Finally, the kinetic data for the polymerization of n-hexyl isocyanate and the known chemistry of CpTiCl2L compounds were found to be consistent with a propagation step that occurs via a bifunctional activation mechanism.

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