Antipyrine complexes of titanium(IV), zirconium(iv), thorium(IV) and uranium(VI) perchlorates

Antipyrine complexes of TiO2+, ZrO2+, Zr4+, Th4+ and UO2+2 perchlorates with molecular formulae TiO(Apy)4(ClO4)2, ZrO(Apy)3(ClO4)2, Zr(Apy)6(ClO4)4, Th(Apy)7(ClO4)4 and UO2(Apy)5(ClO4)2 have been prepared and characterized. The complexes are stable in air at room temperature and decompose exothermally at ~3OO °C. The i.r. study indicates the bonding of the antipyrine to the metal ion through its carbonyl oxygen. The nature of the bonding of the perchlorate and the stereochemistry of the complexes are discussed in the light of infrared spectra, conductivity in solvents of different polarity, and molecular weight measurements. From the UO2+2 group frequencies, the force constant K and rU-o are found to be 6.29 × 105 dynes/ cm-1 and 1.74 Å, respectively.

Preparation, characterization and photophysical properties of layered zirconium bis(monohydrogenphosphate) intercalated with rare earth complexes

Two kinds of rare earth (RE) complexes were intercalated into zirconium bis(monohydrogenphosphate) (alpha -ZrP) by exchanging the RE complexes into the p-methyoxyaniline (PMA) preintercalated compound Zr(O3POH)(2). 2PMA (alpha -ZrP . 2PMA). Powder X-ray diffraction patterns reveal that Eu(DBM)(3)phen (DBM: dibenzoylmethane, phen: 1,10-phenanthroline) and Tb(AA)(3)phen (AA: acetylacetone) intercalated into alpha -ZrP . 2PMA. This was confirmed by the UV-visible spectra of both the RE complexes and the assemblies. At the same time, the assemblies have better luminescent properties, and the fluorescent lifetimes of RE3+ in the excited state in the assemblies are much longer than those in the complexes. The stabilities of the assemblies under UV radiation are much better than those of the RE complexes.

The anions [(ZrOH(CO3)3)2]6− and [(ZrOH(C2O4)3)2]6−: single crystal X-ray diffraction studies of the complexes guanidinium zirconium carbonate [(C(NH2)3)3ZrOH(CO3)3·H2O]2 and sodium zirconium oxalate Na6(ZrOH(C2O4)3)2·7H2O

The complex [(C(NH2)3)3ZrOH(CO3)3·H2O]2 (A) has been shown by means of a single crystal X-ray diffraction study to contain [C(NH2)3]+ cations and dimeric anions of formulation [(ZrOH(CO3)3)2]6−. The anion is centrosymmetric with each metal being bonded to two bridging OH groups and three chelating CO2−3 ions. The Zr atoms are thus eight coordinate with a dodecahedral environments. The ZrO distances formed by the bridgng OH groups are shorter than those formed through zirconiu carbonate interactions. The non-bonded Zr…Zr distance is 3.47(2) Å. An infrared spectroscopic investigation of A provides data which support the findings of the crystallographic study. Likewise the complex Na6(ZrOH(CO2O4)3)2·7H2O (B) contains the anion [(ZrOH(C2O4)3)2]6−. This anion is structurally related to the anion in A as each Zr atom has an eight-coordinate dodecahedral environment being bonded to two bridging OH groups and three chelating oxalate ligands, but has no imposed crysallographic symmetry. The Zr…Zr non-bonded distance is 3.50(1) Å. The OZrO bridge angles are 69.7(4)° and A and 67.4(3)° in B.

Fulvalene cyclopentadienyl titanium and zirconium(III) and -(IV) complexes. X-Ray crystal structure of [{Ti(η5-C5H5) Cl}2 (μ-O)(μ-η5-η5-C10H8)]

The reaction of the fulvalene titanium(III) hydride [{Ti(η5-C5H5)(μ-H)}2(μ-η5-η5-C10H8)] (1) with chlorine leads to [{Ti(η5-C5H5)(μ-Cl)}2(μ-η5-η5-C10H8)] (3) and [{Ti(η5-C5H5)Cl2}2(μ-η5-η5-C10H8)] (4). The reaction of 3 with azobenzene, in wet toluene, gives [{Ti(η5-C5H5)Cl}2(μ-O)(μ-η5-η5-C10H8)] (5) and 1,2-diphenyl hydrazine. The alkylation of 4 and the analogous zirconium complex [{Zr(η5-C5H55)Cl2}2(μ-η5-η5-C10H8)] (2) with LiCH2SiMe3 or LiCH3 permits isolation of the tetraalkyl derivatives [{M(η5-C5H5)(CH2SiMe3)2}2(μ-η5-η5-C10H8)] (M  Ti (6); Zr (8)) and [{Ti(η5-C5H5)(CH3)2}2(μ-η5-η5C10H8)] (7). All the new fulvalene compounds were characterized by IR, and 1H and 13C NMR spectroscope, and mass spectra and 5 by X-ray diffraction. The structure of 5 is very similar to that of the comparable TiIV compound [{Ti(η5-C5H5)2Cl}2(μ-O)] except for the smaller TiOTi angle (159.4° against 173.81°) and a significant deviation from linearity.

Synthetic, structural and mechanistic studies of interactions of carbon, nitrogen, and oxygen nucleophiles with bis-pentamethylcyclopentadienyl zirconium and hafnium derivatives

The reactivity of permethylzirconocene and permethylhafnocene complexes with various nucleophiles has been investigated. Permethylzirconocene reacts with sterically hindered ketenes and allenes to afford metallacycle products. Reaction of these cummulenes with permethylzirconocene hydride complexes affords enolate and σ-allyl species, respectively. Reactions which afford enolate products are nonstereospecific, whereas reactions which afford allyl products initially give a cis-σ-allyl complex which rearranges to its trans isomer. The mechanism of these reactions is proposed to occur either by a Lewis Acid-Lewis Base interaction (ketenes) or by formation of a π-olefin intermediate (allenes).

Permethylzirconocene haloacyl complexes react with strong bases such as lithium diisopropylamide or methylene trimethylphosphorane to afford ketene compounds. Depending on the size of the alkyl ketene substituent, the hydrogenation of these compounds affords enolate-hydride products with varying degrees of stereoselectivity. The larger the substituent, the greater is the selectivity for cis hydrogenation products.

The reaction of permethylzirconocene dihydride and permethylhafnocene dihydride with methylene trimethylphosphorane affords methyl-hydride and dimethyl derivatives. Under appropriate conditions, the metallated-ylide complex 1, (η^5-C_5(CH_3)_5)_2 Zr(H)CH_2PMe_2CH_2, is also obtained and has been structurally characterized by X-ray diffraction techniques. Reaction of 1 with CO affords (η^5-C_5(CH_3)_5)_2 Zr(C,O-η^2 -(PMe_3)HC=CO)H which exists in solution as an equilibrium mixture of isomers. In one isomer (2), the η^2-acyl oxygen atom occupies a lateral equatorial coordination position about zirconium, whereas in the other isomer (3), the η-acyl oxygen atom occupies the central equatorial position. The equilibrium kinetics of the 2→3 isomerization have been studied and the structures of both complexes confirmed by X-ray diffraction methods. These studies suggest a mechanism for CO insertion into metal-carbon bonds of the early transition metals.

Permethylhafnocene dihydride and permethylzirconocene hydride complexes react with diazoalkanes to afford η^2-N, N' -hydrazonido species in which the terminal nitrogen atom of the diazoalkane molecule has inserted into a metal-hydride or metal-carbon bond. The structure of one of these compounds, Cp*_2Zr(NMeNCTol_2)OH, has been determined by X-ray diffraction techniques. Under appropriate conditions, the hydrazonido-hydride complexes react with a second equivalent of diazoalkene to afford η' -N-hydrazonido-η^2-N, N' -hydrazonido species.

Bis(thiophenolate)pyridine pincer ligands and trivalent zirconocene complexes relevant to early transition metal polymerization catalysts

Two major topics are covered: the first chapter is focused on the development of post-metallocene complexes for propylene polymerization. The second and third chapters investigate the consequences of diisobutylaluminum hydride (HAlⁱBu₂) additives in zirconocene based polymerization systems.

The synthesis, structure, and solution behavior of early metal complexes with a new tridentate LX₂ type ligand, bis(thiophenolate)pyridine ((SNS) = (2-C₆H₄S)₂-2,6-C₅H₃N) are investigated. SNS complexes of Ti, Zr, and Ta having dialkylamido coligands were synthesized and structurally characterized. The zirconium complex, (SNS)Zr(NMe₂)₂, displays C₂ symmetry in the solid state. Solid-state structures of tantalum complexes (SNS)Ta(NMe₂)₃ and (SNS)TaCl(NEt₂)₂ also display pronounced C₂ twisting of the SNS ligand. 1D and 2D NMR experiments show that (SNS)Ta(NMe₂)₃ is fluxional with rotation about the Ta N(amide) bonds occurring on the NMR timescale. The fluxional behavior of (SNS)TaCl(NEt₂)₂ in solution was also studied by variable temperature ¹H NMR. Observation of separate signals for the diastereotopic protons of the methylene unit of the diethylamide indicates that the complex remains locked on the NMR timescale in one diastereomeric conformation at temperatures below -50 °C.

Reduction of Zr(IV) metallocenium cations with sodium amalgam (NaHg) produces EPR signals assignable to Zr(III) metallocene complexes. Thus, chloro-bridged heterobinuclear ansa-zirconocenium cation [((SBI))Zr(μ-Cl)₂AlMe₂]⁺B(C₆F₅)_4¯ (SBI = rac-dimethylsilylbis(1-indenyl)), gives rise to an EPR signal assignable to the complex (SBI)Zr^III(μ-Cl)₂AlMe₂, while (SBI)Zr^III-Me and (SBI)Zr^III(-H)2AlⁱBu₂ are formed by reduction of [(SBI)Zr(μ-Me)₂AlMe₂]⁺B(C₆F₅)_4¯ and [(SBI)Zr(μ-H)₃(AlⁱBu₂)₂]⁺B(C₆F₅)4¯, respectively. These products are also formed, along with (SBI)Zr^III-ⁱBu and [(SBI)Zr^III]⁺ AlR4¯ when (SBI)ZrMe₂ reacts with HAlⁱBu₂, eliminating isobutane en route to the Zr(III) complex. Studies concerning the interconversion reactions between these and other (SBI)Zr(III) complexes and reaction mechanisms involved in their formation are also reported.

The addition of HAlⁱBu₂ to precatalyst [(SBI)Zr(µ-H)₃(AlⁱBu₂)₂]⁺ significantly slows the polymerization of propylene and changes the kinetics of polymerization from 1st to 2nd order with respect to propylene. This is likely due to competitive inhibition by HAlⁱBu₂. When the same reaction is investigated using [(ⁿBuCp)₂Zr(μ-H)₃(AlⁱBu₂)₂]⁺, hydroalumination between propylene and HAlⁱBu₂ is observed instead of propylene polymerization.

Ancillary ligand effects : from zirconium(IV)-catalyzed homogeneous propylene polymerization to platinum(II)-mediated C-H bond activation

A series of C_s- and C₁-symmetric doubly-linked ansa-metallocenes of the general formula {1,1'-SiMe₂-2,2'-E-('ƞ⁵-C₅H₂-4-R¹)-(ƞ⁵-C₅H-3',5'-(CHMe₂)₂)}ZrC₂ (E = SiMe₂ (1), SiPh₂ (2), SiMe₂ -SiMe₂ (3); R¹ = H, CHMe₂, C₅H₉, C₆H₁₁, C₆H₅) has been prepared. When activated by methylaluminoxane, these are active propylene polymerization catalysts. 1 and 2 produce syndiotactic polypropylenes, and 3 produces isotactic polypropylenes. Site epimerization is the major pathway for stereoerror formation for 1 and 2. In addition, the polymer chain has slightly stronger steric interaction with the diphenylsilylene linker than with the dimethylsilylene linker. This results in more frequent site epimerization and reduced syndiospecificity for 2 compared to 1.

C₁-Symmetric ansa-zirconocenes [1,1 '-SiMe₂-(C₅H₄)-(3-R-C₅H₃)]ZrCl₂ (4), [1,1 '-SiMe₂-(C₅H₄)-(2,4-R₂-C₅H₂)]ZrCl₂ (5) and [1,1 '-SiMe₂-2,2 '-(SiMe₂-SiMe₂)-(C₅H₃)-( 4-R-C₅H₂)]ZrCl₂ (6) have been prepared to probe the origin of isospecificity in 3. While 4 and 3 produce polymers with similar isospecificity, 5 and 6 give mostly hemi-isotactic-like polymers. It is proposed that the facile site epimerization via an associative pathway allows rapid equilibration of the polymer chain between the isospecific and aspecific insertion sites. This results in more frequent insertion from the isospecific site, which has a lower kinetic barrier for chain propagation. On the other hand, site epimerization for 5 and 6 is slow. This leads to mostly alternating insertion from the isospecific and aspecific sites, and consequently, a hemi-isotactic-like polymers. In comparison, site epimerization is even slower for 3, but enchainment from the aspecific site has an extremely high kinetic barrier for monomer coordination. Therefore, enchainment occurs preferentially from the isospecific site to produce isotactic polymers.

A series of cationic complexes [(ArN=CR-CR=NAr)PtMe(L)]⁺[BF₄]⁺ (Ar = aryl; R = H, CH₃; L = water, trifluoroethanol) has been prepared. They react smoothly with benzene at approximately room temperature in trifluoroethanol solvent to yield methane and the corresponding phenyl Pt(II) cations, via Pt(IV)-methyl-phenyl-hydride intermediates. The reaction products of methyl-substituted benzenes suggest an inherent reactivity preference for aromatic over benzylic C-H bond activation, which can however be overridden by steric effects. For the reaction of benzene with cationic Pt(II) complexes, in which the diimine ligands bear 3,5-disubstituted aryl groups at the nitrogen atoms, the rate-determining step is C-H bond activation. For the more sterically crowded analogs with 2,6-dimethyl-substituted aryl groups, benzene coordination becomes rate-determining. The more electron-rich the ligand, as reflected by the CO stretching frequency in the IR spectrum of the corresponding cationic carbonyl complex, the faster the rate of C-H bond activation. This finding, however, does not reflect the actual C-H bond activation process, but rather reflects only the relative ease of solvent molecules displacing water molecules to initiate the reaction. That is, the change in rates is mostly due to a ground state effect. Several lines of evidence suggest that associative substitution pathways operate to get the hydrocarbon substrate into, and out of, the coordination sphere; i.e., that benzene substitution proceeds by a solvent- (TFE-) assisted associative pathway.

Self-immobilized titanium and zirconium catalysts with phenoxy-imine ligands for ethylene polymerization. X-ray crystal structure of bis(N-(3-tert-butylsalicylidene)-4 '-allyloxyanilinato) zirconium(IV) dichloride

Four self-immobilized FI catalysts with allyl substituted phenoxy-imine ligands [{4-(CH2=CHCH2O)C6H5N=CH-C6H3(3-tert-C4H9)O}(2) MCl2] (1: M = Ti: 2: M = Zr), [{3-(CH2=CHCH2O)C6H5N=CH-C6H3(3-tert-C4H9)O}(2)MCl2] (3: M = Zr), [{4-(CH2=CHCH2-2,6-(iso-C3H7)(2))C6H5N=CH-C6H3(3,5-(NO2)(2))O}(2)MCl2] (4: M = Zr) have been synthesized and characterized. The molecular structure of 2 has been determined by X-ray crystallographic analysis. The results of ethylene polymerization showed that the self-immobilized titanium (IV) and zirconium (IV) catalysts 1-3 kept high activity for ethylene polymerization and 4 showed no activity. SEM showed the immobilization effect could greatly improve the morphology of polymer particles to afford micron-granula polyolefin as supported catalysts.

Synthesis, structure and ethylene polymerization of group 4 complexes with phosphinoamide ligands

Group 4 complexes containing diphosphinoamide ligands [Ph2PNR](2)MCl2 (3: R = Bu-t, M = Ti; 4: R = Bu-t, M = Zr; 5: R = Ph, M = Ti; 6: R = Ph, M = Zr) were prepared by the reaction Of MCl4 (M = Ti; Zr) with the corresponding lithium phosphinoamides in ether or THF. The structure of [(Ph2PNBu)-Bu-t](2)TiCl2 (3) was determined by X-ray crystallography. The phosphinoamides functioned as eta(2)-coordination ligands in the solid state and the Ti-N bond length suggests it is a simple single bond. In the presence of modified methylaluminoxane or i-Bu3Al/Ph3BC(C6F5)(4), catalytic activity of up to 59.5 kg PE/mol cat h bar was observed.

Ansa-metallocene derivatives .2. Syntheses and structures of tetramethyldisiloxandiyl bis(1-indenyl and tetrahydroindenyl) zirconium dichlorides

The ansa-zirconocene derivative tetramethyldisiloxandiyl bis(1-indenyl) zirconium dichloride (1) has been prepared by the reaction of the dilithium salt of 1,3-bis(l-indenyl) tetramethyldisiloxane with ZrCl4 . 2THF, After catalytic hydrogenation, the corresponding tetrahydroindenyl complex (2) has been formed. Both 1 and 2 have been shown by H-1 NMR spectra to be the mixture of the cis(meso) and trans(rac) isomers, The pure trans isomers 1(l), 2(l) and cis isomer 2(c) were obtained by recrystallization, The crystal structures of 1(l) and 2(c) were determined by X-ray diffraction. Both crystals of 1(l) and 2(c) are monoclinics, belonging to space groups P2(1)/n(1(l)) and P2(1)/c(2(c)). In the unit cell of 2(c), one of the six-membered rings of the tetrahydroindenyl Ligands has two different conformations which have the same probabilities.

SYNTHESIS, PROPERTIES AND MOLECULAR-STRUCTURE OF 5-COORDINATE N,N-DIBENZYLDITHIOCARBAMATE COMPLEXES OF TITANOCENE, ZIRCONOCENE AND HAFNOCENE

The five complexes (RC5H4)2M(S2CNBz2)Cl (R = H, CH3; M = Ti, Zr, Hf; Bz = CH2C6H5) have been prepared by the reaction of (RC5H4)2MCl2 with anhydrous sodium salts of dibenzyldithiocarbamate in refluxing CH2Cl2. These complexes have been characterized by elemental analysis, IR and H-1 NMR. X-ray crystal structure determination of Cp2Zr(S2CNBZ2)Cl shows the molecule has a five-coordinate bent metallocene geometry in which the zirconium atom is attached to two eta-5-C5H5 groups, one bidentate dibenzyldithiocarbamate ligand and one chlorine [Zr-Cl, 2.549(1) angstrom; Zr-S, 2.734(1), 2.667(1); Cl-Zr-S, 137.6(1)-degrees and 73.3(1)-degrees; S-Zr-S, 64.3(1)-degrees]. The catalytic system Cp2Ti (S2CNBZ2)Cl-NaH exhibits high initial catalytic activity of hydrogenation of hexene-1 under mild conditions.

Investigation of ideal zirconium-doped perovskite-type ceramic membrane materials for oxygen separation

Zirconium-doped perovskite-type membrane materials of BaCo0.4Fe0.6-xZrxO3-delta (x = 0-0.4) with mixed oxygen ion and electron conductivity were synthesized through a method of combining citric and EDTA acid complexes. The results of X-ray diffraction (XRD), oxygen temperature-programmed desorption (O-2-TPD) and hydrogen temperature-programmed reduction (H-2-TPR) showed that the incorporation of proper amount of zirconium into BaCo0.4Fe0.6O3-delta could stabilize the ideal and cubic structure of perovskite. Studies on the oxygen permeability of the as-synthesized membrane disks under air/He gradient indicated that the content of zirconium in these materials had great effects on oxygen permeation flux, activation energy for oxygen permeation and operation stability. The high oxygen permeation flux of 0.90 ml cm(-2) min(-1) at 950degreesC, the single activation energy for oxygen permeation in the range of 600-950 degreesC and the long-term operation stability at a relatively lower operational temperature of 800 degreesC under air/He gradient were achieved for the BaCo0.4Fe0.4Zr0.2O3-delta material. Meanwhile, the effect of carbon dioxide on structural stability and oxygen permeability of this material was also studied in detail, which revealed that the reversible stability could be attained for it. (C) 2002 Elsevier Science B.V. All rights reserved.

A novel zirconium-based perovskite-type membrane material for oxygen permeation

A novel zirconium-based membrane material of BaCo0.4Fe0.4Zr0.2O3-6 with cubic perovskite structure was synthesized for the first time through a method of citric and EDTA acid combined complexes. The structural stability was characterized by XRD, O-2-TPD and H-2-TPR techniques respectively. The high oxygen permeation flux of 0.873 mL/cm(2) min at 950 degreesC was obtained under He/Air gradient. Meanwhile, the single activation energy for oxygen permeation and the long-term steady operation of 200 h at 800 degreesC were achieved.

Electrochemistry of Heteroleptic Tris(phthalocyaninato) Rare Earth(III) Complexes

The electrochemical characteristics of a series of heteroleptic tris(phthalocyaninato) complexes with identical rare earths or mixed rare earths (Pc)M(OOPc)M(OOPc) [M = Eu...Lu, Y; H2Pc = unsubstituted phthalocyanine, H2(OOPc) = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] and (Pc)Eu(OOPc)Er(OOPc) have been recorded and studied comparatively by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetrabutylammonium perchlorate (TBAP). Up to five quasi-reversible one-electron oxidations and four one-electron reductions have been revealed. The half-wave potentials of the first, second and fifth oxidations depend on the size of the metal center, but the fifth changes in the opposite direction to that of the first two. Moreover, the difference in redox potentials of the first oxidation and first reduction for (Pc)M(OOPc)M(OOPc), 0.85−0.98 V, also decreases linearly along with decreasing rare earth ion radius, clearly showing the rare earth ion size effect and indicating enhanced π−π interactions in the triple-deckers connected by smaller lanthanides. This order follows the red-shift seen in the lowest energy band of triple-decker compounds. The electronic differences between the lanthanides and yttrium are more apparent for triple-decker sandwich complexes than for the analogous double-deckers. By comparing triple-decker, double-decker and mononuclear [ZnII] complexes containing the OOPc ligand, the HOMO−LUMO gap has been shown to contract approximately linearly with the number of stacked phthalocyanine ligands.