New aluminum and gallium complexes of β-diketiminato and β-ketiminato ligands

Jana, Barun; Uhl, Werner

doi:10.1016/j.ica.2016.10.013

Cited by 18 publications

(27 citation statements)

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“…23. A similar structure has been obtained in the literature for a Ph NacNac aluminum species (which contains one "normal" Ph NacNac ligand and one reduced Ph NacNac ligand),241 and exists likely due to an intramolecular hydroalumination reaction that occurs during precursor synthesis. The TGA of 8 (Figure 5.21c)demonstrates that the compound is thermally stable, but is less volatile than compound 6 which can be observed by its higher onset of volatilization.…”

supporting

confidence: 67%

Design and development of group 13 precursors for improved vapour deposition of metal nitride thin films

Buttera¹

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supporting

confidence: 67%

Design and development of group 13 precursors for improved vapour deposition of metal nitride thin films

Buttera¹

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“…The reduction process was revealed in the reaction of NacNacH with AlH 3 and EtNMe 2 , in which the reduced ligand was formed by hydrogen atom transfer from aluminum to a β-carbon atom. 60 4b [{(Ar)NC(CH 2 )CH=C(Me)(P-P t Bu 2 )}Ti=NAr(Cl)] − [Li(12-crown-4) 2 ] + ·(Et 2 O) can be considered as a product of hydrogen elimination from the Me group at the β-carbon atom in the NP hybrid ligand. In the 1 H NMR spectrum, the two protons of the methylene group are observed at 2.96 and 2.63 ppm.…”

Section: Results and Discussionmentioning

confidence: 99%

Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu₂P–P(SiMe₃) Ligand

et al. 2020

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We present two important trends in the reactivity of the titanium complex [ Me NacNacTi(Cl){η 2 -P(SiMe 3 )-P t Bu 2 }] ( Me NacNac – = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6- i Pr 2 Ph) with nucleophilic reagents RLi (R = Ph 2 P, t BuO, (Me 3 Si) 2 N, and t Bu 2 N) depending on the reaction medium. Reaction in nonpolar solvent (toluene) leads to three main products: via an autoredox process and nucleophilic substitution at the Ti-atom to afford the Ti(IV) complex [ Me NacNacTi(R){η 2 -P-P t Bu 2 }] ( 1 for R = PPh 2 ), via the elimination of Me 3 SiR to afford Ti(III) complex [ Me NacNacTi(Cl){η 2 -P-P t Bu 2 }] − [Li(12-crown-4) 2 ] + ( 2 ), and via 2e – reduction process to afford new ionic complex [{ArNC(Me)CHC(Me)}Ti=NAr{η 1 -P(SiMe 3 )-P t Bu 2 }] − [Li(12-crown-4) 2 ] + ( 3 ). Quite differently, the complex [ Me NacNacTi(Cl){η 2 -P(SiMe 3 )-P t Bu 2 }] reacts with Ph 2 PLi in THF, unexpectedly yielding two new, four-coordinate Ti(IV) imido complexes 4a [{ArNC(Me)=CHC(H)(Me)-P(P t Bu 2 )}Ti=NAr(Cl)] − [Li(12-crown-4) 2 ] + ·(toluene) 2 and 4b [{ArNC(CH 2 )CH=C(Me)-P(P t Bu 2 )}Ti=NAr(Cl)] − [Li(12-crown-4) 2 ] + ·(Et 2 O). Complex 2 dissolved in THF converts to 4a and 4b . 1 , 2 , 3 , 4a , and 4b were characterized by X-ray diffraction. 1 , 4a , and 4b were also fully characterized by multinuclear NMR spectroscopy.

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“…13,20,21 The majority of these studies employ β-diketiminate ligands with sterically demanding N–Ar substituents (e.g., Ar = 2,6- i Pr 2 C 6 H 3 ) that shield the Al center, but recently derivatives with less bulky groups were described. 22−24 An unusual low-valent aluminum(I) compound with sterically demanding β-diketiminate ligand was prepared by Roesky and co-workers via potassium reduction of the diiodide complex (Scheme 1A). 25…”

Section: Introductionmentioning

confidence: 99%

Aluminum Complexes with Redox-Active Formazanate Ligand: Synthesis, Characterization, and Reduction Chemistry

Mondol

Otten

2019

Inorg. Chem.

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The synthesis of aluminum complexes with redox-active formazanate ligands is described. Salt metathesis using AlCl3 was shown to form a five-coordinate complex with two formazanate ligands, whereas organometallic aluminum starting materials yield tetrahedral mono(formazanate) aluminum compounds. The aluminum diphenyl derivative was successfully converted to the iodide complex (formazanate)AlI2, and a comparison of spectroscopic/structural data for these new complexes is provided. Characterization by cyclic voltammetry is supplemented by chemical reduction to demonstrate that ligand-based redox reactions are accessible in these compounds. The possibility to obtain a formazanate aluminum(I) carbenoid species by two-electron reduction was examined by experimental and computational studies, which highlight the potential impact of the nitrogen-rich formazanate ligand on the electronic structure of compounds with this ligand.

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New aluminum and gallium complexes of β-diketiminato and β-ketiminato ligands

Cited by 18 publications

References 50 publications

Design and development of group 13 precursors for improved vapour deposition of metal nitride thin films

Design and development of group 13 precursors for improved vapour deposition of metal nitride thin films

Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu₂P–P(SiMe₃) Ligand

Aluminum Complexes with Redox-Active Formazanate Ligand: Synthesis, Characterization, and Reduction Chemistry

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New aluminum and gallium complexes of β-diketiminato and β-ketiminato ligands

Cited by 18 publications

References 50 publications

Design and development of group 13 precursors for improved vapour deposition of metal nitride thin films

Design and development of group 13 precursors for improved vapour deposition of metal nitride thin films

Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu2P–P(SiMe3) Ligand

Aluminum Complexes with Redox-Active Formazanate Ligand: Synthesis, Characterization, and Reduction Chemistry

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Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu₂P–P(SiMe₃) Ligand