Synthesis and Characterization of Ti Complexes Using 4‐tert‐Butyl‐2,6‐bis(hydroxymethyl)phenol: X‐ray Structures of a Confacial Bioctahedron with Terminal Nucleophilic Phenylmethoxide Ligands, and a Ti4O16 Core Protected by Two Hydrophobic Binding Pockets

Glaser, Thorsten; Liratzis, Ioannis; Lügger, Thomas; Fröhlich, Roland

doi:10.1002/ejic.200300921

Cited by 10 publications

(10 citation statements)

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“…[4,5] It must be noted that the facesharing bridging mode in confacial bioctahedra is defined by single bridging donor atoms, e.g. [12] Herein, we present the new dinucleating ligand H 6 ioan, which is suitable for the synthesis of heterodinuclear confacial bioctahedra. μ 1,3 -N 3 or RNOof oximes.…”

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The First Heterotrinuclear Confacial Trioctahedron Ni^IITi^IVCr^III: Rational Modular Assembly and Cooperative Effects

et al. 2015

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The heterodinuclear complex [(ioan)Ni II Ti IV ] with a facial O 3 donor set of Ti IV -coordinated benzyl alcoholates serves as a metallo-ligand for a {Cr III Cl 3 } fragment to yield the heterotri-The interaction between metal ions is the major determinant for the construction of molecule-based magnetic materials, [1] for electron-transfer in molecular wires, [2] and for the cooperativity in catalysis of polynuclear active sites either in synthetic or biological systems. [3] For complexes without direct metal-metal bonding, the metal-metal interaction depends on the covalency of the bridging ligandmetal bond and on the nature of the bridging mode mode: corner-, edge-or face-sharing. The triple-bridged facesharing bridging mode is the less frequently observed bridging mode in octahedrally coordinated complexes (facesharing bioctahedron). This has been attributed to the short metal-metal distance, which may lead to repulsive cationcation interactions. [4,5] It must be noted that the facesharing bridging mode in confacial bioctahedra is defined by single bridging donor atoms, e.g. Cl -, RO -, μ 1,1 -N 3 -, not e.g. μ 1,3 -N 3 or RNOof oximes. The short metal-metal separation in face-sharing octahedral complexes leads to interestinig electronic properties, [6] especially in mixedvalence complexes, where delocalized class III systems [7] have been observed that exhibit high-spin ground states by the double exchange mechanism. [8,9] In our continuous efforts to enforce ferromagnetic interactions and high spin ground states, [10] we have started a synthetic project to establish metallo-ligands, [11] which are capable of leading to supramolecular chains of face-sharing octahedra exhibiting double exchange. [12] Herein, we present the new dinucleating ligand H 6 ioan, which is suitable for the synthesis of heterodinuclear confacial bioctahedra. [a] 912 nuclear complex [(ioan)Ni II Ti IV Cr III Cl 3 ]. Comparisons of their molecular structures and electrochemical properties exhibit strong cooperative effects between the metal ions.They are intended to serve as metallo-ligands by their benzyl alcoholate O 3 face to coordinate a third metal ion. This results in the first confacial trioctahedron with three different metal ions.The ligand H 6 ioan is prepared by the tris-Schiff-base condensation of the tris-amine 1 [13] with three equivalents of the aldehyde 2 (Scheme 1). [14] The heterodinuclear complex [(ioan)NiTi] has been obtained by successive treatment of the ligand with Ni II acetate and Ti IV butoxide. The reaction of the metalloligand [(ioan)NiTi] with [CrCl 3 (thf) 3 ] results in the heterotrinuclear complex [(ioan)NiTiCrCl 3 ] (Figure 1, a). Although a complex with three different metal ions have reported by the metallo-ligands strategy, [15] [(ioan)NiTiCrCl 3 ] is the first confacial trioctahedron with three different metal ions. Scheme 1. Synthesis of the ligand and the complexes.

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The First Heterotrinuclear Confacial Trioctahedron Ni^IITi^IVCr^III: Rational Modular Assembly and Cooperative Effects

et al. 2015

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“…[ 22 ] The interaction of 4‐ tert ‐butyl‐2,6‐bis‐(hydroxymethyl)‐phenol derivatives with TiO(acac) 2 leads to the formation of anionic clusters of compositions (Et 4 N) [L 3 Ti 2 ] or (Et 4 N) 2 [L 2 (HL) 4 Ti 4 O 2 ]. [ 23 ]…”

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confidence: 99%

Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF₃‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene

Тuskaev

Гагиева

Bogdanov

et al. 2021

Applied Organom Chemis

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The coordination chemistry of a new compartmental ligand 2,6‐(bis‐CF3‐carbinol)‐4‐tert‐butylphenol with Ti(IV) and Zr(IV) has been studied. The structures of Al, Ti, and Zr complexes with the participation of this ligand were established by X‐ray diffraction. Upon activation with Et2AlCl or Et3Al2Cl3 and Bu2Mg, Ti(IV) complex exhibited moderate catalytic activity for ethylene polymerization. The obtained UHMWPE samples were processed into high‐strength (up to 2.7 GPa) and high‐modulus (up to 162 GPa) films through solid‐phase molding and orientation drawing. The mononuclear and binuclear Ti(IV) complexes catalyzed the ternary copolymerization of ethylene, propylene, and 5‐ethylidene‐norbornene. Tercopolymers with a content of propylene units up to 36 mol% and 5‐EBN up to 8.6 mol% were synthesized with a high activity (2.8–6.3 tons of copolymer/mol Ti h); the mechanical characteristics of elastomeric materials have been studied.

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“…[24] Our intention is to obtain a synthetic access to an isostructural series of confacial pentaoctahedra that allows the targeted variation of the transition metal center and hence to study the properties of such an unprecedented family of complexes with short metal-metal distances by the face-sharing bridging motive in dependence of the individual d n electron configurations. Our synthetic strategy implied first the synthesis of confacial bioctahedra [25] as metallo-ligand building blocks, that can coordinate with one site to a central metal ion in the second step to provide confacial pentaoctahedra. For this reason, we have designed the ligand H 6 ioan (Scheme 2a), which provides a N 3 O 3 and an O 6 ligand compartment.…”

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Rational Design of a Confacial Pentaoctahedron: Anisotropic Exchange in a Linear Zn^IIFe^IIIFe^IIIFe^IIIZn^II Complex

Walleck

Atanasov

Schnack

et al. 2021

Chemistry A European J

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The first confacial pentaoctahedron comprised of transition metal ions namely Zn II Fe III A Fe III B Fe III A Zn II has been synthesized by using a dinucleating nonadentate ligand. The face-sharing bridging mode enforces short Zn II •••Fe III A and Fe III A •••Fe III B distances of 2.83 and 2.72 Å, respectively. Ab-initio CASSCF/NEVPT2 calculations provide significant negative zero-field splittings for Fe III A and Fe III B with j D A j > j D B j with the main component along the C 3 axis. Hence, a spin-Hamiltonian comprised of anisotropic exchange, zero-field, and Zeeman term was employed. This allowed by following the boundary conditions from the theoretical results the simulation in a theory-guided parameter determination with J xy = + 0.37, J z = À 0.32, D A = À 1.21, E A = À 0.24, D B = À 0.35, and E B = À 0.01 cm À 1 supported by simulations of high-field magnetic Mössbauer spectra recorded at 2 K. The weak but ferromagnetic Fe III A Fe III B interaction arises from the small bridging angle of 84.8°being at the switch from anti-to ferromagnetic for the face-sharing bridging mode.

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Synthesis and Characterization of Ti Complexes Using 4‐tert‐Butyl‐2,6‐bis(hydroxymethyl)phenol: X‐ray Structures of a Confacial Bioctahedron with Terminal Nucleophilic Phenylmethoxide Ligands, and a Ti₄O₁₆ Core Protected by Two Hydrophobic Binding Pockets

Cited by 10 publications

References 39 publications

The First Heterotrinuclear Confacial Trioctahedron Ni^IITi^IVCr^III: Rational Modular Assembly and Cooperative Effects

The First Heterotrinuclear Confacial Trioctahedron Ni^IITi^IVCr^III: Rational Modular Assembly and Cooperative Effects

Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF₃‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene

Rational Design of a Confacial Pentaoctahedron: Anisotropic Exchange in a Linear Zn^IIFe^IIIFe^IIIFe^IIIZn^II Complex

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Synthesis and Characterization of Ti Complexes Using 4‐tert‐Butyl‐2,6‐bis(hydroxymethyl)phenol: X‐ray Structures of a Confacial Bioctahedron with Terminal Nucleophilic Phenylmethoxide Ligands, and a Ti4O16 Core Protected by Two Hydrophobic Binding Pockets

Cited by 10 publications

References 39 publications

The First Heterotrinuclear Confacial Trioctahedron NiIITiIVCrIII: Rational Modular Assembly and Cooperative Effects

The First Heterotrinuclear Confacial Trioctahedron NiIITiIVCrIII: Rational Modular Assembly and Cooperative Effects

Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF3‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene

Rational Design of a Confacial Pentaoctahedron: Anisotropic Exchange in a Linear ZnIIFeIIIFeIIIFeIIIZnII Complex

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Synthesis and Characterization of Ti Complexes Using 4‐tert‐Butyl‐2,6‐bis(hydroxymethyl)phenol: X‐ray Structures of a Confacial Bioctahedron with Terminal Nucleophilic Phenylmethoxide Ligands, and a Ti₄O₁₆ Core Protected by Two Hydrophobic Binding Pockets

The First Heterotrinuclear Confacial Trioctahedron Ni^IITi^IVCr^III: Rational Modular Assembly and Cooperative Effects

The First Heterotrinuclear Confacial Trioctahedron Ni^IITi^IVCr^III: Rational Modular Assembly and Cooperative Effects

Binuclear Ti(IV) complex with new compartmental ligand 2,6‐(bis‐CF₃‐carbinol)‐4‐tert‐butylphenol as precatalysts for ethylene polymerization and its copolymerization with propylene and 5‐ethylidene‐norbornene

Rational Design of a Confacial Pentaoctahedron: Anisotropic Exchange in a Linear Zn^IIFe^IIIFe^IIIFe^IIIZn^II Complex