Organoaluminum Compounds

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (31 August 2020) | Viewed by 30360

Special Issue Editors


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Guest Editor
Department of Quantum Beam Science, Graduate School of Science and Engineering, Ibaraki University, Hitachi, Ibaraki 316-8511, Japan
Interests: organoelement chemistry; organometallic chemistry; polymer chemistry; material chemistry

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Guest Editor
Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan
Interests: low-valent heavier main group element compounds; multiple bonds of heavier main group elements; main group element catalysis

Special Issue Information

Dear Colleagues,

Organoaluminum compounds bearing AlIII atoms have been commonly used in organic, organometallic, and inorganic chemistry as Lewis acids, reductants, and nucleophiles. Meanwhile, novel organometallic compounds consisting of low-oxidation state (AlI or AlII) or multiply bonded aluminum atoms have been recently developed as bottleable species. Their structure and properties are attracting broad interest, because of their potential as new building blocks in organometallic chemistry and main group metal-based catalyst. In addition, a number of new organic and inorganic reactions using organoaluminum compounds bearing AlIII atoms have being reported. The aim of this special issue is to display the recent progress in the experimental and theoretical studies on the syntheses, structures, reactivities, and catalytic application of organoaluminum compounds bearing low-oxidation state (AlI or AlII) as well as common oxidation state (AlIII) aluminum atoms. This issue is associated with the development of novel synthetic methodologies, structural elucidations, bonding analysis, and applications in stoichiometric or catalytic molecular transformations using organoaluminum compounds and aluminum-containing complexes. New methodology in organic or inorganic syntheses using organoaluminum compounds is also welcomed.

Prof. Dr. Tomohiro Agou
Prof. Dr. Norihiro Tokitoh
Guest Editors

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Keywords

  • Low-oxidation state organoaluminum compounds
  • Common oxidation state organoaluminum compounds
  • Multiple bonds containing aluminum atoms
  • Aluminum complexes with unique structure, reactivities, and catalytic activity
  • Organic or inorganic molecular transformations using organoaluminum reagents or catalyst
  • Main group metal-based catalysts

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Published Papers (7 papers)

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Research

10 pages, 2017 KiB  
Article
Mono- and Dinuclear Aluminium Complexes Derived from Biguanide and Carbothiamide Ligands
by Maximilian Dehmel, Helmar Görls and Robert Kretschmer
Inorganics 2021, 9(7), 52; https://doi.org/10.3390/inorganics9070052 - 7 Jul 2021
Cited by 2 | Viewed by 3071
Abstract
Dianionic N,N-chelating ligands play a crucial role in coordination chemistry, but reports on related complexes remain limited to certain types of ligands. In here, the reactions of two diprotic ligands, i.e., a biguanide and a carbothiamide, with trimethylaluminium, are reported, which give rise [...] Read more.
Dianionic N,N-chelating ligands play a crucial role in coordination chemistry, but reports on related complexes remain limited to certain types of ligands. In here, the reactions of two diprotic ligands, i.e., a biguanide and a carbothiamide, with trimethylaluminium, are reported, which give rise to mono- and dinuclear aluminium(III) complexes. In addition, single deprotonation of the diprotic biguanide using potassium bis(trimethylsilyl)amide gives rise to a one-dimensional coordination polymer. All complexes have been fully characterized, and their solid-state structures were determined by single crystal X-ray diffraction analysis. Full article
(This article belongs to the Special Issue Organoaluminum Compounds)
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10 pages, 2952 KiB  
Communication
A PAlP Pincer Ligand Bearing a 2-Diphenylphosphinophenoxy Backbone
by Kazuhiko Semba, Ikuya Fujii and Yoshiaki Nakao
Inorganics 2019, 7(12), 140; https://doi.org/10.3390/inorganics7120140 - 28 Nov 2019
Cited by 18 | Viewed by 4217
Abstract
A PAlP pincer ligand derived from 2-diphenylphosphino-6-isopropylphenol was synthesized. The Lewis acidity of the Al center of the ligand was evaluated with coordination of (O)PEt3. A zwitterionic rhodium-aluminum heterobimetallic complex bearing the PAlP ligand was synthesized through its complexation with [RhCl(nbd)] [...] Read more.
A PAlP pincer ligand derived from 2-diphenylphosphino-6-isopropylphenol was synthesized. The Lewis acidity of the Al center of the ligand was evaluated with coordination of (O)PEt3. A zwitterionic rhodium-aluminum heterobimetallic complex bearing the PAlP ligand was synthesized through its complexation with [RhCl(nbd)]2. Moreover, reduction of the zwitterionic rhodium-aluminum complex with KC8 afforded heterobimetallic complexes bearing an X-type PAlP pincer ligand. Full article
(This article belongs to the Special Issue Organoaluminum Compounds)
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12 pages, 2450 KiB  
Article
Syntheses and Structures of Novel λ33-Phosphanylalumanes Fully Bearing Carbon Substituents and Their Substituent Effects
by Tatsuya Yanagisawa, Yoshiyuki Mizuhata and Norihiro Tokitoh
Inorganics 2019, 7(11), 132; https://doi.org/10.3390/inorganics7110132 - 7 Nov 2019
Cited by 7 | Viewed by 2990
Abstract
The novel phosphanylalumanes, Al–P single-bond species, fully bearing carbon protecting groups on aluminum and phosphorus atoms, are synthesized by the reactions of aluminum monohalides [(t-Bu)2AlBr and (C6F5)2AlCl·0.5(toluene)] with Mes2PLi. Regarding the [...] Read more.
The novel phosphanylalumanes, Al–P single-bond species, fully bearing carbon protecting groups on aluminum and phosphorus atoms, are synthesized by the reactions of aluminum monohalides [(t-Bu)2AlBr and (C6F5)2AlCl·0.5(toluene)] with Mes2PLi. Regarding the t-Bu system, λ33-phosphanylalumane is obtained. Concerning the C6F5 system, on the other hand, the corresponding LiCl complex, λ44-phosphanylalumane, is obtained. The Al–P bond lengths of C6F5-substituted λ34-, and λ44-derivatives are much shorter than those of the reported λ34-phosphanylalumane derivatives and comparable to that observed for the previously reported λ33-phosphanylalumanes. Theoretical calculations reveal that the binding of the C6F5 groups to Al results in a large contribution of Al and a large s-character in the Al–P bond of phosphanylalumanes. Considering t-Bu-substituted phosphanylalumanes, the Al–P bond lengths reflect the coordination number of Al, showing a longer Al–P bond length in the case of λ4-Al as compared with that of λ3-Al. Combining the structural, spectroscopic, and theoretical results, the t-Bu-substituted λ33-phosphanylalumane has well separated vacant p orbital and lone pairs, which is suitable for reactivity studies. Full article
(This article belongs to the Special Issue Organoaluminum Compounds)
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13 pages, 2919 KiB  
Article
Reaction of Dialumane Incorporating Bulky Eind Groups with Pyridines
by Takahiro Murosaki, Ryoma Ohno, Tomohiro Agou, Daisuke Hashizume and Tsukasa Matsuo
Inorganics 2019, 7(11), 129; https://doi.org/10.3390/inorganics7110129 - 25 Oct 2019
Cited by 3 | Viewed by 2945
Abstract
The reaction of the bulky Eind-based dialumane, (Eind)HAl(μ-H)2AlH(Eind) (1) (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl), with pyridines is described. When 1 was treated with pyridine (Py) in toluene, the Py adduct of aryldihydroalumane, Py→AlH2(Eind) (2 [...] Read more.
The reaction of the bulky Eind-based dialumane, (Eind)HAl(μ-H)2AlH(Eind) (1) (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl), with pyridines is described. When 1 was treated with pyridine (Py) in toluene, the Py adduct of aryldihydroalumane, Py→AlH2(Eind) (2), was initially formed. Then, the hydroalumination of Py took place to yield the Py-bound aryl(1,4-dihydropyrid-1-yl)hydroalumane, Py→AlH(1,4-dihydropyrid-1-yl)(Eind) (3). A similar reaction with a stronger Lewis base, 4-pyrrolidinopyridine (PPy), produced the stable PPy adduct, PPy→AlH2(Eind) (4). The resulting organoaluminum compounds have been fully characterized by NMR spectroscopy as well as X-ray crystallography. The reaction mechanism from 1 to 3 via 2 has been examined by deuterium labeling experiments using (Eind)DAl(μ-D)2AlD(Eind) (1-d4). Full article
(This article belongs to the Special Issue Organoaluminum Compounds)
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13 pages, 2638 KiB  
Communication
Propeller-Shaped Aluminum Complexes with an Azaperylene Core in the Ligands
by Masahiro Tsukao, Yoshifumi Hashikawa, Nana Toyama, Masahiro Muraoka, Michihisa Murata, Takahiro Sasamori, Atsushi Wakamiya and Yasujiro Murata
Inorganics 2019, 7(9), 109; https://doi.org/10.3390/inorganics7090109 - 3 Sep 2019
Cited by 1 | Viewed by 5966
Abstract
Tris(8-hydroxyquinoline) aluminum(III) (Alq3) and its derivatives, characterized by a propeller-shaped three-dimensionally π-conjugated structure, have been intensively studied in the few past decades on account of their potential utility in optoelectronic applications. Reported herein are the synthesis and properties of π-extended Alq [...] Read more.
Tris(8-hydroxyquinoline) aluminum(III) (Alq3) and its derivatives, characterized by a propeller-shaped three-dimensionally π-conjugated structure, have been intensively studied in the few past decades on account of their potential utility in optoelectronic applications. Reported herein are the synthesis and properties of π-extended Alq3 complexes that contain an azaperylene core in each ligand. Intramolecular palladium-catalyzed direct C–H arylations or base-promoted arylations were employed to prepare these large Alq3 analogues. A single-crystal X-ray diffraction analysis of one of the obtained Al complexes revealed a unique three-dimensional packing structure within the crystal, i.e., a honeycomb packing along the ab-plane and columnar π-stacks along the c-axis. An Alq3 analogue with azaperylene-dicarboximide ligands exhibited deep blue color in solution with an intense absorption band that extended to 780 nm (λmax = 634 nm; ε = 58,000 M−1 cm−1). Full article
(This article belongs to the Special Issue Organoaluminum Compounds)
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15 pages, 3883 KiB  
Article
Characterization and Photophysical Properties of a Luminescent Aluminum Hydride Complex Supported by a β-Diketiminate Ligand
by Shunichiro Ito, Kazuo Tanaka and Yoshiki Chujo
Inorganics 2019, 7(8), 100; https://doi.org/10.3390/inorganics7080100 - 17 Aug 2019
Cited by 23 | Viewed by 4446
Abstract
Aluminum hydrides are versatile compounds utilized as reducing agents, precursors of aluminum complexes, and as catalysts for polymerization reactions. However, their photophysical properties have been overlooked, although several luminescent aluminum complexes have been utilized conventionally for emitting layers in modern light-emitting devices. Herein, [...] Read more.
Aluminum hydrides are versatile compounds utilized as reducing agents, precursors of aluminum complexes, and as catalysts for polymerization reactions. However, their photophysical properties have been overlooked, although several luminescent aluminum complexes have been utilized conventionally for emitting layers in modern light-emitting devices. Herein, we report the synthesis and photophysical properties of a luminescent β-diketiminate dihydride complex through the reaction between lithium aluminum hydride and the corresponding ligand. The obtained compound exhibits crystallization-induced emission (CIE) properties at room temperature and long-lifetime phosphorescence at 80 K. Our experimental and theoretical investigations suggest that low-energy molecular vibration could play an important role in the realization of the CIE property. Full article
(This article belongs to the Special Issue Organoaluminum Compounds)
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11 pages, 2029 KiB  
Communication
NHI- and NHC-Supported Al(III) Hydrides for Amine–Borane Dehydrocoupling Catalysis
by Catherine Weetman, Nozomi Ito, Masafumi Unno, Franziska Hanusch and Shigeyoshi Inoue
Inorganics 2019, 7(8), 92; https://doi.org/10.3390/inorganics7080092 - 24 Jul 2019
Cited by 10 | Viewed by 4744
Abstract
The catalytic dehydrocoupling of amine–boranes has recently received a great deal of attention due to its potential in hydrogen storage applications. The use of aluminum catalysts for this transformation would provide an additional cost-effective and sustainable approach towards the hydrogen economy. Herein, we [...] Read more.
The catalytic dehydrocoupling of amine–boranes has recently received a great deal of attention due to its potential in hydrogen storage applications. The use of aluminum catalysts for this transformation would provide an additional cost-effective and sustainable approach towards the hydrogen economy. Herein, we report the use of both N-heterocyclic imine (NHI)- and carbene (NHC)-supported Al(III) hydrides and their role in the catalytic dehydrocoupling of Me2NHBH3. Differences in the σ-donating ability of the ligand class resulted in a more stable catalyst for NHI-Al(III) hydrides, whereas a deactivation pathway was found in the case of NHC-Al(III) hydrides. Full article
(This article belongs to the Special Issue Organoaluminum Compounds)
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