Aluminum Complexes Containing Cyclohexane‐1,2‐diyl Linked Bis(ketiminato) Ligands and Proton‐Promoted Demethylation

Huang, Chun‐Hsueh; Hsueh, Li‐Feng; Kuo, Pei-Cheng; Lee, Hon Man; Uno, Chia‐Liang; Huang, Jui‐Hsien; Tu, Cheng‐Yi; Hu, Ching‐Han; Lee, Gene‐Hsiang; Hung, Chen‐Hsiung

doi:10.1002/ejic.200800057

Cited by 11 publications

(1 citation statement)

References 38 publications

(33 reference statements)

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“…LiNMeEt was prepared by the addition of HNMeEt to a solution n ‐BuLi in hexanes at −78 °C and the removal of all volatiles after stirring at room temperature overnight to obtain the desired product as a white solid. Cis ‐ and H 2 ( trans ‐Cyacen) were prepared using the same method as H 2 (acen) (similar to the previously reported method, but starting with pure cis ‐ or trans ‐1,2‐diaminocyclohexane) [39] . The proligands H 2 (acen), H 2 ( cis ‐Cyacen), and H 2 ( trans ‐Cyacen) were dissolved in toluene and dried over 4 Å molecular sieves for 2 weeks before use.…”

Section: Methodsmentioning

confidence: 99%

Synthesis, Structures, and Thermal Stability of Dialkyl and Bis(amido) Zirconium(IV) Acen Complexes

Hareri

Emslie

2022

Eur J Inorg Chem

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Reaction of one equivalent of H 2 (acen), H 2 (cis-Cyacen) or H 2 (trans-Cyacen) with [Zr(CH 2 SiMe 3 ) 4 ] at room temperature afforded [Zr(acen)(CH 2 SiMe 3 ) 2 ] (1), [Zr(cis-Cyacen)(CH 2 SiMe 3 ) 2 ] (2) or [Zr(trans-Cyacen)(CH 2 SiMe 3 ) 2 ] (3), respectively (acen = C 2 H 4 (NCMeCHC(O)Me) 2 ; Cyacen = 1,2-C 6 H 10 (NCMeCHC(O)Me) 2 ). These alkyl compounds are trigonal prismatic in the solid state, and whereas 1 and 3 decomposed without sublimation above 120 °C (5-10 mTorr), 2 sublimed in > 95 % yield at 85 °C (5-10 mTorr). However, heating solid 2 at 88 °C under static argon for 24 hours resulted in extensive decomposition to afford H 2 (cis-Cyacen) and SiMe 4 as the soluble products. Compound 2 reacted cleanly with two equivalents of t BuOH to afford [Zr(cis-Cyacen)(O t Bu) 2 ] (4), but excess t BuOH caused both SiMe 4 and H 2 (cis-Cyacen) elimination. The 1 : 1 reaction of H 2 (acen) with [Zr(NMeEt) 4 ] did not proceed cleanly, and 8-coordinate [Zr-(acen) 2 ] (5) was identified as a by-product; this complex was isolated from the 2 : 1 reaction. A zirconium amido complex, [Zr(acen)(NMeEt) 2 ] (6) was accessed via the reaction of 1 with two equiv. or excess HNMeEt, but decomposed readily in solution at room temperature. More sterically hindered [Zr-(acen){N(SiMe 3 ) 2 } 2 ] (7) was synthesized via the reaction of [Zr(acen)Cl 2 ] with two equivalents of Li{N(SiMe 3 ) 2 }, but was also thermally unstable as a solid and in solution at room temperature. Compounds 1-3, 5 and 7 were crystallographically characterized.

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Section: Methodsmentioning

confidence: 99%

Synthesis, Structures, and Thermal Stability of Dialkyl and Bis(amido) Zirconium(IV) Acen Complexes

Hareri

Emslie

2022

Eur J Inorg Chem

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Ketiminate‐Supported LiCl Cages and Group 13 Complexes

Lugo

Richards

2010

Eur J Inorg Chem

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The coordination preferences of the ketiminato ligands L1H, {[RN(H)(C(Me))2C(Me)=O], R = 2,6‐diisopropylphenyl (Dipp) or 2,6‐dimethylphenyl (Dmp)} and L2H {[RN(H)C(Me)CHC(Me)=O], R = C2H4NEt2} with group 13 elements were investigated. The expected N,O‐chelated products [DmpL1BF2] (1), [L2Al(Me)Cl] (2A and 2B), and [L2InMe2] (6), were obtained from reactions with BF3·OEt2, AlMe2Cl and InMe3 respectively, but the reaction of DippL1 with GaCl3 afforded a metal‐halide, neutral ligand adduct, [GaCl3·DippL1H] (3). More interestingly the reactions of DippL1 with InMe3, formed in situ from InCl3 and MeLi, led to the isolation of two ketiminate‐supported LiCl cages[InMe2Li7Cl5(DippL1–)2(DippL1)(THF)3] (4) and [Li5(Cl)(DippL1)4]·2PhMe (5). The lithium cage 4 features reaction of InMe3 with one backbone methyl group from each of two DippL1 ligands, to afford a tetraalkylindate moiety in the framework of two doubly deprotonated ligands (L–).

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Synthesis and structural characterization of monomeric aluminum keto‐imine complexes: Catalytic activity toward CO₂/styrene oxide coupling and ε‐caprolactone ring opening polymerization

et al. 2023

J Chinese Chemical Soc

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A series of benzoylacetone-imine ligands, PhCOCHCMeNHR (L 1 H, R = CH 2 Ph; L 2 H, R = CH 2 Ph-4-Me; and L 3 H, R = CH 2 Ph-4-OMe), are first synthesized following the condensation of benzoylacetone and 4-substituted benzylamine. Later, reacting L 1 H-L 3 H with one equivalent of AlMe 3 in toluene, the monomeric Al derivatives are generated, (PhCOCHCMeNR)AlMe 2 (1, R = CH 2 Ph; 2, R = CH 2 Ph-4-Me; 3, R = CH 2 Ph-4-OMe). All the ligands and metal derivatives are characterized by 1 H and 13 C NMR spectroscopy. Single crystal X-ray diffraction analysis reveals the geometry of all ligands and complex 2. As supporting catalysts, the Al derivatives, 1-3, are effective to initiate the coupling of CO 2 and styrene oxide to form cyclic carbonates. Although employing TBAI (tetra-nbutylammonium iodide), TBAC, tetrabutylammonium chloride, and TBAB (tetra butyl ammonium bromide) as cocatalyst, the optimized catalytic system exhibits the best conversion of epoxide in presence of TBAI under the reaction temperature and time, respectively, 90 C and 6 hr, respectively. The ring opening polymerization of ε-caprolactone is also appraised subjecting the Al derivatives, 1-3, as catalysts in presence of benzyl alcohol and all the conversions of ε-caprolactone reach over 95% at the reaction condition of 100 C and 1 hr. K E Y W O R D S aluminum, CO 2 -epoxide coupling, keto-imine, ring opening polymerization, ε-Caprolactone

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Aluminum Complexes Containing Cyclohexane‐1,2‐diyl Linked Bis(ketiminato) Ligands and Proton‐Promoted Demethylation

Cited by 11 publications

References 38 publications

Synthesis, Structures, and Thermal Stability of Dialkyl and Bis(amido) Zirconium(IV) Acen Complexes

Synthesis, Structures, and Thermal Stability of Dialkyl and Bis(amido) Zirconium(IV) Acen Complexes

Ketiminate‐Supported LiCl Cages and Group 13 Complexes

Synthesis and structural characterization of monomeric aluminum keto‐imine complexes: Catalytic activity toward CO₂/styrene oxide coupling and ε‐caprolactone ring opening polymerization

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Aluminum Complexes Containing Cyclohexane‐1,2‐diyl Linked Bis(ketiminato) Ligands and Proton‐Promoted Demethylation

Cited by 11 publications

References 38 publications

Synthesis, Structures, and Thermal Stability of Dialkyl and Bis(amido) Zirconium(IV) Acen Complexes

Synthesis, Structures, and Thermal Stability of Dialkyl and Bis(amido) Zirconium(IV) Acen Complexes

Ketiminate‐Supported LiCl Cages and Group 13 Complexes

Synthesis and structural characterization of monomeric aluminum keto‐imine complexes: Catalytic activity toward CO2/styrene oxide coupling and ε‐caprolactone ring opening polymerization

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About

Synthesis and structural characterization of monomeric aluminum keto‐imine complexes: Catalytic activity toward CO₂/styrene oxide coupling and ε‐caprolactone ring opening polymerization