Molecular Structures and NMR Studies of Lithium and Germanium(<scp>II</scp>) Complexes of a New Chelating Amido–Imino Ligand Obtained by Addition of <i>n</i>BuLi to 1,2‐Bis(arylimino)acenaphthene

Fedushkin, Igor L.; Hummert, Markus; Schumann, Herbert

doi:10.1002/ejic.200600265

Cited by 26 publications

(26 citation statements)

References 37 publications

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“…Subsequently, this approach has been extended to include the use of group 13 alkyl reagents for the syntheses of three additional BIAN* complexes (3,4, and 5) (Figure 1). 6 In contrast to the work of Fedushkin et al, 5 a study performed by Hill et al 7 revealed that the reaction of dpp-BIAN with the bulky nucleophile K[CH(SiMe 3 ) 2 ] resulted in the formation of a backbone dearomatized derivative of BIAN*. In this interesting reaction, the [CH(SiMe 3 ) 2 ] − anion functionalized the backbone of the dpp-BIAN molecule, thereby dearomatizing one of the naphthalene rings and generating a different chiral BIAN* complex.…”

Section: ■ Introductionmentioning

confidence: 89%

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Sterically Directed Functionalization of the Redox-Active Bis(imino)acenaphthene Ligand Class: An Experimental and Theoretical Investigation

2013

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The synthesis, characterization, and theoretical study of the sterically directed functionalization of the redox-active bis(imino)acenaphthene (BIAN) ligand class has been explored. With dependence on the steric congestion encompassing the N-C-C-N fragment of the Ar-BIAN ligand, functionalization can be directed to proceed either via a radical backbone dearomatization or a nucleophilic imine C-alkylation pathway. The structures of the Ar-BIAN derivatives 14-19 were determined by means of single-crystal X-ray diffraction. The reaction pathways involved in Ar-BIAN functionalization were monitored by means of EPR spectroscopy. The experimental results and observations were examined in conjunction with DFT-D calculations in order to explain the driving forces that direct the pathways leading to Ar-BIAN functionalization.

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Section: ■ Introductionmentioning

confidence: 89%

“…The first such reaction of this type was reported by Fedushkin et al 5 and resulted in formation of a novel chiral nbutylated amido-imine lithium BIAN* complex (2) (BIAN* = amido-imine BIAN). A consequence of adopting the direct imine C-alkylation pathway is preservation of the backbone aromaticity of the functionalized BIAN* molecule.…”

Section: ■ Introductionmentioning

confidence: 95%

Sterically Directed Functionalization of the Redox-Active Bis(imino)acenaphthene Ligand Class: An Experimental and Theoretical Investigation

2013

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“…IR spectra were measured from compound suspensions in the Vaseline oil on a FSM 1201 spectrometer. 1 [(1 Allyl 2 (2,6 diisopropylphenylimino) 1,2 dihydroace naphthylen 1 yl){2,6 diisopropylphenyl}amino]aluminum bromo iodide (8). Ether solution containing AlI 3 (0.14 g, 0.33 mmol) (or I 2 (0.13 g, 0.5 mmol)) and dpp BIAN (0.50 g, 1.0 mmol) was added to fine powdered aluminum foil.…”

Section: Methodsmentioning

confidence: 99%

“…An anionic amido imine ligand [Bu n -dpp BIAN] -can be transferred from lithium to other metals, e.g., germanium(II) 8 and zinc(II). 9 The analogous alkaline earth metal complexes are also known.…”

mentioning

confidence: 99%

“…7 Lithium complexes containing chiral amido imine ligand are obtained by reacting dpp BIAN with butyl lithium (Scheme 1). 8 The reactions involve the addition of Bu n Li to one of the two C=N double bonds of a ligand, where an n butyl radical adds to the imine carbon and a lithium atom -to the nitrogen, yielding the lithium salt of unsymmetrical chelating amido imine ligand.…”

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Synthesis and structure of novel chiral amido-imine complexes of aluminum, gallium, and indium

et al. 2009

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The reactions of 1,2 bis[(2,6 diisopropylphenyl)imino]acenaphthene (dpp BIAN, 1) with tri iso butylaluminum, triethylgallium or trimethylindium give the novel amido imine com plexes (Bu i -dpp BIAN)AlBu i 2 (4), (Et-dpp BIAN)GaEt 2 (5), and (Me-dpp BIAN)InMe 2 (6), respectively. The reaction of (dpp BIAN)AlI(Et 2 O) (7) with allyl bromide affords analo gous chiral amido imine derivative (All-dpp BIAN)AlBrI (8). Hydrolysis of 8 affords the amino imino compound (All-dpp BIAN)H (9). The new compounds 4-6, 8, and 9 have been characterized by 1 H NMR and IR spectroscopy. The molecular structures of 5, 6, and 9 were determined by single crystal X ray analysis.

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Redox‐Active Ligand‐Assisted Two‐Electron Oxidative Addition to Gallium(II)

Fedushkin

Dodonov

Skatova

et al. 2018

Chemistry A European J

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The reaction of digallane (dpp-bian)Ga-Ga(dpp-bian) (2) (dpp-bian=1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) with allyl chloride (AllCl) proceeded by a two-electron oxidative addition to afford paramagnetic complexes (dpp-bian)Ga(η -All)Cl (3) and (dpp-bian)(Cl)Ga-Ga(Cl)(dpp-bian) (4). Treatment of complex 4 with pyridine induced an intramolecular redox process, which resulted in the diamagnetic complex (dpp-bian)Ga(Py)Cl (5). In reaction with allyl bromide, complex 2 gave metal- and ligand-centered addition products (dpp-bian)Ga(η -All)Br (6) and (dpp-bian-All)(Br)Ga-Ga(Br)(dpp-bian-All) (7). The reaction of digallane 2 with Ph SnNCO afforded (dpp-bian)Ga(SnPh ) (8) and (dpp-bian)(NCO)Ga-Ga(NCO)(dpp-bian) (9). Treatment of GaCl with (dpp-bian)Na in diethyl ether resulted in the formation of (dpp-bian)GaCl (10). Diorganylgallium derivatives (dpp-bian)GaR (R=Ph, 11; tBu, 14; Me, 15; Bn, 16) and (dpp-bian)Ga(η -All)R (R=nBu, 12; Cp, 13) were synthesized from complexes 3, 10, Bn GaCl, or tBu GaCl by salt metathesis. The salt elimination reaction between (dpp-bian)GaI (17) and tBuLi was accompanied by reduction of both the metal and the dpp-bian ligand, which resulted in digallane 2 as the final product. Similarly, the reaction of complex 10 with MentMgCl (Ment=menthyl) proceeded with reduction of the dpp-bian ligand to give the diamagnetic complex [(dpp-bian)GaCl ][Mg Cl (THF) ] (18). Compounds 11, 12, 13, 15, and 16 were thermally robust, whereas compound 14 decomposed when heated at reflux in toluene to give complex (dpp-bian-tBu)GatBu (19). Both complexes 7 and 19 contain R-substituted dpp-bian ligand: in the former compound the allyl group was attached to the imino-carbon atom, whereas in complex 19, the tBu group was situated on the naphthalene ring. Crystal structures of complexes 3, 8, 9, 10, 13, 14, 18, and 19 were determined by single-crystal X-ray analysis. The presence of dpp-bian radical anions in 3, 6, 8, and 10-16 was determined by ESR spectroscopy.

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Molecular Structures and NMR Studies of Lithium and Germanium(II) Complexes of a New Chelating Amido–Imino Ligand Obtained by Addition of nBuLi to 1,2‐Bis(arylimino)acenaphthene

Cited by 26 publications

References 37 publications

Sterically Directed Functionalization of the Redox-Active Bis(imino)acenaphthene Ligand Class: An Experimental and Theoretical Investigation

Sterically Directed Functionalization of the Redox-Active Bis(imino)acenaphthene Ligand Class: An Experimental and Theoretical Investigation

Synthesis and structure of novel chiral amido-imine complexes of aluminum, gallium, and indium

Redox‐Active Ligand‐Assisted Two‐Electron Oxidative Addition to Gallium(II)

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