Addition of Enolisable Ketones to (dpp‐bian)Mg(THF)<sub>3</sub> [dpp‐bian =1,2‐Bis{(2,6‐diisopropylphenyl)imino}acenaphthene]

Fedushkin, Igor L.; Skatova, Alexandra A.; Fukin, Georgy K.; Hummert, Markus; Schumann, Herbert

doi:10.1002/ejic.200400948

Cited by 51 publications

(23 citation statements)

References 23 publications

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“…In spite of the difference in the positions of the Me 3 Si substituents at the double carbon-nitrogen bonds, the C-N and Si-N distances are virtually identical (see Table 3). The C-N bond lengths (1.2702 (19) and 1.2637(19) Å) are similar to the corresponding distances in 1,2 bis[(2,6 diisopropyl phenyl)imino]acenaphthene (both bond lengths are 1.282(4) Å). 25 The C(1)-C(2) distance (1.5478(18) Å) in the structure of 1 corresponds to the single car bon-carbon bond length.…”

Section: Methodsmentioning

confidence: 65%

New acenaphthene-1,2-diimine and its reduction to the tetraanion. Molecular structures of 1,2-bis[(trimethylsilyl)imino]acenaphthene and its lithium derivatives

et al. 2006

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1,2 Bis[(trimethylsilyl)imino]acenaphthene (1) was synthesized by the reaction of acenaphthenequinone with (Me 3 Si) 2 NLi in toluene followed by treatment of the reaction product with trimethylchlorosilane. The dianionic derivative [(tms BIAN)Li 2 ] 2 (3) was ob tained as the final product by reduction of compound 1 with lithium in toluene, whereas reduction in diethyl ether afforded the tetraanion [(tms BIAN)Li 4 (Et 2 O) 3 ] 2 (5). The forma tion of the paramagnetic mono and trianions in solution was confirmed by ESR spectroscopy. Compounds 3 and 5 were isolated in the crystalline state and characterized by elemental analysis, IR spectroscopy, and NMR spectroscopy. The crystal structures of 1, 3, and 5 were established by X ray diffraction.In the last decade, acenaphthene 1,2 diimines (BIAN) have been widely used as ligands in coordination chemis try. Transition metal complexes with diimine ligands are efficient catalysts for alkyne hydrogenation, 1 carbon-car bon bond formation, 2 cycloisomerization, 3 hydrosilyla tion, 4 polymerization of alkenes 5 and acrylic mono mers, 6 and copolymerization of CO 2 and methylenecyclo propene, 7 ethylene, norbornene, 8 and styrene. 9 Acenaphthenediimine complexes of transition metals (Brookhart catalysts) are the most efficient olefin poly merization catalysts. 10 The π acceptor properties of acenaphthene 1,2 diimines in metal complexes induce an electron deficiency at the metal atom, which is re sponsible for high reactivity of these complexes toward organic compounds.Earlier, we have demonstrated that main group met als, unlike transition metals, can form complexes with different anionic forms of BIAN ligands. We used prima rily 1,2 bis[(2,6 diisopropylphenyl)imino]acenaphthene (dpp BIAN), which shows variable oxidation states in complexes with main group metals. Diimine dpp BIAN can be reduced with alkali metals in ethereal media to the mono , di , tri , and tetraanions to form the [(dpp BIAN)M n (Et 2 O) n ] salts (M = Li or Na; n = 1-4). 11In THF, alkaline earth metals reduce dpp BIAN only to the dianion to give the monomeric (dpp BIAN)M(THF) n complexes (M = Mg, Ca, Sr, or Ba; n = 2-4). 12 Reduc tion of dpp BIAN with aluminum metal in the presence of halides in toluene or Et 2 O affords the radical anionic compound (dpp BIAN)AlCl 2 and the dianionic products (dpp BIAN)AlI(Et 2 O) and (dpp BIAN)AlCl(Et 2 O), re spectively. 13 We synthesized aluminum alkyl complexes with both the radical anion and the dianion of dpp BIAN by the metathesis reactions of the corresponding so dium derivatives of dpp BIAN with alkylaluminum halides. 14 The metathesis of sodium salts of three dif ferent acenaphthene 1,2 diimines with GeCl 2 gave the germanium(II) compounds (BIAN)Ge 15 and (dpp BIAN)GeCl. 16 The (dpp BIAN)Mg(thf) 3 complex acts as a one elec tron reducing agent for organic halides 17 and aromatic ketones. 18 The reactions of (dpp BIAN)Mg(thf) 3 with compounds containing a mobile hydrogen atom, for ex ample, with aliphatic ketones, 19 nitriles, 12b or phenyl acetylene, 20 i...

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Section: Methodsmentioning

confidence: 65%

New acenaphthene-1,2-diimine and its reduction to the tetraanion. Molecular structures of 1,2-bis[(trimethylsilyl)imino]acenaphthene and its lithium derivatives

et al. 2006

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“…In magnesium23 and aluminum24 complexes, dpp‐BIAN may be present either as a chelating radical‐anionic or chelating dianionic ligand ( A and B , respectively). Magnesium complexes with amido/amino23b,23f,23h and amido/imino23j ligands derived from dpp‐BIAN are also reported ( C and D , respectively). As a result of the bulkiness of dpp‐BIAN, its monomeric metal complexes are typical, for example, (dpp‐BIAN)Mg(thf) 3 ( 1 ),23a (dpp‐BIAN)Mg i Pr(Et 2 O),23e and (dpp‐BIAN)AlMe(Et 2 O) 24d…”

Section: Introductionmentioning

confidence: 91%

Magnesium(II) Complexes of the dpp‐BIAN Radical‐Anion: Synthesis, Molecular Structure, and Catalytic Activity in Lactide Polymerization

et al. 2009

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Reaction of (dpp-BIAN)Mg(THF) 3 (1) {dpp-BIAN = 1,2-bis [(2,6-diisopropylphenyl)imino]acenaphthene} with one molar equivalent of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) proceeds with oxidation of the dpp-BIAN dianion in 1 to the radical-anion and affords the (dpp-BIAN)-Mg(TEMPO)(thf) (2) complex. The reaction of dpp-BIAN with an excess amount of magnesium and 0.5 molar equivalents of I 2 in Et 2 O gives (dpp-BIAN)MgI(Et 2 O) n , which then reacts in situ with (Me 3 Si) 2 NK to produce (dpp-BIAN)-Mg[N(SiMe 3 ) 2 ](Et 2 O) (3). Solvent-free magnesium amide (dpp-BIAN)Mg[N(SiMe 3 ) 2 ] (4) was synthesized by treating equimolar amounts of MgI 2 , dpp-BIAN, and sodium in tolu-

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“…The reactivity of two representative examples (dpp‐bian)Mg(THF) 3 ( 1 ) and (dpp‐bian)Ga−Ga(dpp‐bian) ( 2 ) has been studied thoroughly. We observed the following reactivity modes for compound 1 : 1) addition of substrates through the one‐electron oxidation of the ligand, which results in a magnesium–substrate bond, 2) addition of organic halides R−X to both the ligand and metal to afford L −R and M−X bonds, and 3) addition of terminal alkynes, nitriles, and enols by protonation of dianionic dpp‐bian ligand, which results in magnesium acetylenides, keteniminates, and enolates –. In contrast, compound 2 reacts with different alkynes to form cycloadducts that liberate “coordinated” alkyne upon heating .…”

Section: Introductionmentioning

confidence: 99%

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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Addition of Enolisable Ketones to (dpp‐bian)Mg(THF)₃ [dpp‐bian =1,2‐Bis{(2,6‐diisopropylphenyl)imino}acenaphthene]

Cited by 51 publications

References 23 publications

New acenaphthene-1,2-diimine and its reduction to the tetraanion. Molecular structures of 1,2-bis[(trimethylsilyl)imino]acenaphthene and its lithium derivatives

New acenaphthene-1,2-diimine and its reduction to the tetraanion. Molecular structures of 1,2-bis[(trimethylsilyl)imino]acenaphthene and its lithium derivatives

Magnesium(II) Complexes of the dpp‐BIAN Radical‐Anion: Synthesis, Molecular Structure, and Catalytic Activity in Lactide Polymerization

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

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Addition of Enolisable Ketones to (dpp‐bian)Mg(THF)3 [dpp‐bian =1,2‐Bis{(2,6‐diisopropylphenyl)imino}acenaphthene]

Cited by 51 publications

References 23 publications

New acenaphthene-1,2-diimine and its reduction to the tetraanion. Molecular structures of 1,2-bis[(trimethylsilyl)imino]acenaphthene and its lithium derivatives

New acenaphthene-1,2-diimine and its reduction to the tetraanion. Molecular structures of 1,2-bis[(trimethylsilyl)imino]acenaphthene and its lithium derivatives

Magnesium(II) Complexes of the dpp‐BIAN Radical‐Anion: Synthesis, Molecular Structure, and Catalytic Activity in Lactide Polymerization

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

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Addition of Enolisable Ketones to (dpp‐bian)Mg(THF)₃ [dpp‐bian =1,2‐Bis{(2,6‐diisopropylphenyl)imino}acenaphthene]