Synthesis and characterization of sterically crowded aryloxides: ‘Mitsubishi’-class of tetrametallic aluminum complexes

Konishi, Akihito; Nakajima, Hideto; Maruyama, Hikaru; Yoshioka, Setsuko; Baba, Akio; Yasuda, Makoto

doi:10.1016/j.poly.2016.10.019

Cited by 6 publications

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References 45 publications

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“…Previous work by Scott and ourselves demonstrated that the trimeric 2 or tetrameric 3 aluminum complexes were dominantly formed (Figure C). Herein, we report the synthesis and characterization of monomeric aluminum complexes with cage-shaped triphenolic ligands (Figure D-ii).…”

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confidence: 68%

“…For the monomeric complexation of the aluminum source with 1 H 3 , some extra attention was required. The direct treatment of 1 H 3 with AlMe 3 in CH 2 Cl 2 was attempted, but this approach gave a trimeric complex by the indication of the NMR measurements. Alternatively, the gradual addition of a solution of 1 H 3 in CH 2 Cl 2 into the pretreated solution of AlMe 3 with the stoichiometric pyridine in CH 2 Cl 2 furnished the desired monomeric aluminum aryl oxide 1 Al as a pyridine complex ( 1 Al·py).…”

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confidence: 99%

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Synthesis of Cage-Shaped Aluminum Aryloxides: Efficient Lewis Acid Catalyst for Stereoselective Glycosylation Driven by Flexible Shift of Four- to Five-Coordination

et al. 2019

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Monomeric cage-shaped aluminum aryl oxides 1Al were synthesized using tripodal triphenolic ligands. The Lewis acidity and catalytic activity of the obtained 1Al•py were investigated. The Lewis acidity of 1Al•py originates from the flexible change in the coordination number of the aluminum center, allowing the catalytic O-glycosylation to occur with a high efficiency and an unusual stereoselectivity.

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confidence: 68%

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confidence: 99%

Synthesis of Cage-Shaped Aluminum Aryloxides: Efficient Lewis Acid Catalyst for Stereoselective Glycosylation Driven by Flexible Shift of Four- to Five-Coordination

et al. 2019

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“…Using aluminum alkyls or halides as precursors, there are two general routes to synthesize organoaluminum complexes, namely salt methathesis or ligand exchange method . Aluminum‐based complexes have been known to render assistance in cycloaddition reactions involving CO 2 fixation and hetero Diels‐Alder reaction …”

Section: Cycloaddition Reactions As a Main Tool For Developing Sustaimentioning

confidence: 99%

Aluminum‐Based Catalysts for Cycloaddition Reactions: Moving One Step Ahead in Sustainability

Dogra

Gupta

2019

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A large variety of dienes and alkenes can be derived from plants and used further for the production of fine chemicals or biologically active compounds. Herein, we have identified such dienes/alkenes, as well as their synthetic analogues, and presented a strategy for their conversion by atom-economical cycloaddition reactions. The catalyst used for these conversions is derived from abundantly-available aluminum metal in earth's crust, which has low toxicity, easy availability and low price in comparison to the transition metals. Astonishingly, the applications of aluminum-based catalysts are underdeveloped in comparison to the d-block metal analogues. Therefore, this review summarizes the developments in the field of cycloaddition reactions by using aluminum-based catalysts, a pathway that can be pursued for developing "Sustainable Processes". . Zeolite (81) catalysed cycloaddition of isoprene with dienes 38 (a-d) Scheme 22. Synthesis of TCPD by oligomerization of DCPD and DCPD oligomer isomerisationReviews

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“…Tetrametallic complexes with a chiral, propeller-like structure similar to that of Werner's "hexol" salts [1][2][3] and of some Group 13 alkoxides and aryloxides [4][5][6][7][8][9][10][11][12][13][14][15][16][17] are of great historical significance in coordination chemistry. When the metal ions carry a spin (s), this metal-centred triangular topology is magnetically appealing, as the ground state has nonzero total spin (S) for both ferro-and antiferromagnetic interactions between the central (M c ) and peripheral (M p ) metal centres.…”

Section: Introductionmentioning

confidence: 99%

Stereoisomerism in Tetrametallic Propeller‐Like Complexes: A Solid‐State and Solution NMR Study on a Tetragallium(III) Derivative

et al. 2021

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Tetragallium(III) complex in [Ga 4 (L 4-Py ) 2 (dpm) 6 ] • EtOH, with H 3 L 4-Py = 2-(hydroxymethyl)-2-(pyridin-4-yl)propane-1,3-diol and Hdpm = dipivaloylmethane, was investigated as a diamagnetic analogue of tetrametallic, propeller-like single-molecule magnets (SMMs). The chiral molecular structure partitions the six CH 2 protons of each tripodal (L 4-Py ) 3À ligand into two diastereotopic sets. The two signals were clearly detected by 1 H NMR spectroscopy in C 6 D 6 , proving that Λ and Δ enantiomers interconvert slowly over NMR timescale. Density functional theory calculations provided quantitative agreement with the observed values of chemical shifts and scalar coupling constants across both geminal and long-range interaction pathways. The solid-state structure suggests the occurrence of a lower symmetry stereoisomer (27 mol%), which was clearly identified in the NMR spectra. Since high spin Fe 3 + forms distinctly more inert complexes than Ga 3 + , comparable or greater configurational stability is expected for the isostructural Fe III 4 , Fe III 3 Cr III , and Fe III 3 V III SMMs, which are difficult to investigate by solution NMR because of the strong paramagnetism.

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Synthesis and characterization of sterically crowded aryloxides: ‘Mitsubishi’-class of tetrametallic aluminum complexes

Cited by 6 publications

References 45 publications

Synthesis of Cage-Shaped Aluminum Aryloxides: Efficient Lewis Acid Catalyst for Stereoselective Glycosylation Driven by Flexible Shift of Four- to Five-Coordination

Synthesis of Cage-Shaped Aluminum Aryloxides: Efficient Lewis Acid Catalyst for Stereoselective Glycosylation Driven by Flexible Shift of Four- to Five-Coordination

Aluminum‐Based Catalysts for Cycloaddition Reactions: Moving One Step Ahead in Sustainability

Stereoisomerism in Tetrametallic Propeller‐Like Complexes: A Solid‐State and Solution NMR Study on a Tetragallium(III) Derivative

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