Addition of Alkynes to a Gallium Bis‐Amido Complex: Imitation of Transition‐Metal‐Based Catalytic Systems

Fedushkin, Igor L.; Nikipelov, Alexander S.; Morozov, A. G.; Skatova, Alexandra A.; Cherkasov, Anton V.; Abakumov, G. A.

doi:10.1002/chem.201102243

Cited by 101 publications

(53 citation statements)

References 72 publications

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“…58, 59 The regioselectivity of the hydroamination products agrees well with a concerted 1,3-dipolar addition with, in the case of the phenylacetylene cycloaddition product, a Ph group pointing away from the Ga(II) center. Amine nucleophilic attack on species 7 occurs and subsequent proton transfer produces the imine final product and regenerates digallane 6.…”

Section: [(Dipp-bian)ga-ga(dipp-bian)]-catalyzed Hydroamination Of Almentioning

confidence: 60%

“…The coupling of vinylarenes with 1,1-diarylethenes in the presence of In(OTf) 3 (10 mol%) produces triarylalkenes (59). The presence of In(III) appears crucial to ensure chemo-and regioselective head-to-tail heterodimerization, presumably thanks to the stabilization of carbocationic species formed during the reaction.…”

Section: Head-to-tail Heterodimerization Of Vinylarenes and 11-diarymentioning

confidence: 99%

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Gallium and Indium Compounds in Homogeneous Catalysis

Dagorne

Fliedel

Frémont

2016

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The present contribution highlights the most recent and representative developments on the use of Ga and In species in homogeneous catalysis. Recent studies of various ligand‐supported Ga(III) and In(III) compounds in cyclic esters polymerization catalysis for the production of biodegradable polyester materials are also included. Various organic transformations may now be catalyzed using Ga(III) and In(III) Lewis acids allowing access to a wide range of valuable organic molecules through diverse reaction sequences. The recent use of stable and robust N ‐heterocyclic carbene Ga(III) and In(III) compounds as strong π‐Lewis acid catalysts for various organic reactions is also discussed: such species are certainly promising for the future developments of Ga(III)‐ and In(III)‐mediated reactions. Although Lewis acid‐assisted reactions certainly dominate the field in Ga(III) and In(III) chemistry, discrete low‐valent In(I) species, presently emerging in catalysis, clearly display a distinct reactivity allowing their exploitation both as soft Lewis acids and alkyl‐/allyl‐/arylating agents.

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Section: [(Dipp-bian)ga-ga(dipp-bian)]-catalyzed Hydroamination Of Almentioning

confidence: 60%

Section: Head-to-tail Heterodimerization Of Vinylarenes and 11-diarymentioning

confidence: 99%

Gallium and Indium Compounds in Homogeneous Catalysis

Dagorne

Fliedel

Frémont

2016

Encyclopedia of Inorganic and Bioinorganic Chemistry

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“…The compound is binuclear and contains two gallium atoms, two o-amidophenolate ligands, and two iodine atoms. [14] The nonbonding repulsion between metal atoms causes the deviation of the Ga (2) Ga (1) 1.395 (4) lengths are less than the sum of the covalent radii of the corresponding elements (Ga-O 1.98 Å, Ga-N 1.99 Å [14] ), which indicates the covalent nature of these bonds. The apexes of tetrahedrons (2) atoms is 2.8743(5) Å, and this value considerably exceeds the sum of gallium covalent radii (2.5 Å).…”

Section: Resultsmentioning

confidence: 99%

“…The reaction mixture was stirred for 2 h, and a color change from wine-red to deep green was observed. 4 Pyridine (2 mL) was added to the resulted solution.…”

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confidence: 99%

The Reduction of Sterically Hindered o‐Quinone and o‐Iminoquinone with Gallium and “GaI”

et al. 2012

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Keywords: Gallium / Quinones / Reduction / EPR spectroscopyMetallic gallium reacts with 3,6-di-tert-butyl-o-benzoquinone (3,6-Q) in THF to produce a gallium tris-o-semiquinolate complex, whereas the same interaction with 4,6di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone (imQ) does not proceed. The reduction of imQ is possible with amalgamed gallium in THF and produces a gallium complex that contains two o-iminobenzoquinone ligands in different redox states. In the case of 3,6-Q, the analogous reaction leads to dimeric derivative [Cat 2 Ga(Et 2 O) 2 ]-[a] G.A. Razuvaev 4318[CatGa] (in which Cat is the dianion of 3,6-Q). The structure of this compound was determined by X-ray diffraction analysis. The gallium(III) amidophenolate derivative can only be obtained by exchange reaction of APNa 2 with GaI 3 (in which AP is the dianion of imQ). The reduction of 3,6-Q and imQ with "GaI" results in the formation of corresponding compounds that contain redox-active ligands in the dianionic state. The structure of [AP 2 Ga][GaI 2 ] was determined by Xray diffraction analysis. Scheme 1. The reaction of digallane with alkynes.o-Quinone and o-Iminoquinone with Gallium and "GaI" One of the most convenient methods of synthesis of metal complexes with redox-active ligands is the direct reduction of o-quinones and their hetero-analogues by metals or metal amalgams. [8] (BIAN)Ga-Ga(BIAN) [9a] and the tris-o-semiquinolate gallium(III) derivatives that contain different o-quinones were synthesized by this method. [6,9b-9d] In some cases, the direct interaction of quinones with gallium leads to the formation of the respective dianionic catecholate derivatives. As reported in the literature, [6] heating of the gallium metal with 1,2-naphthoquinone (NQ) in refluxing toluene results in a deeper reduction of NQ and gives the dimeric catecholate complex [Ga II -(NCat)] 2 (NCat is the dianion of NQ). Catecholate gallium derivatives [(Hal 4 Cat)Ga II ·(phen)] 2 (Hal 4 Cat are dianions of tetrahalo-substituted o-quinones Hal 4 Q; phen = 1,10phenanthroline) form as the result of the reaction of metal with quinones in the presence of phen. [10a] Unfortunately, the authors [6,10a] did not produce sufficient evidence of such structures, and the last ones are questionable. Moreover, the minor product obtained in the reaction of Cl 4 Q with Ga in the presence of phen is the structurally characterized monomeric complex (Cl 4 Cat)GaCl·py·phen (py = pyridine). [10b] It indicates the more complicated nature of the interaction of metallic gallium with Hal 4 Q, which includes elimination of halides from the initial o-quinone.Low-oxidation-state metal derivatives are widely known to reduce 1,2-diketones and related ligands to give chelated compounds with reduced forms of the redox-active ligands. Thus the interaction of benzil with "GaI" results in the formation of a novel trimetallic bis(enediolato) complex. [11a] "GaI" was shown to be a convenient initial reagent for the synthesis of α-diimine gallium derivatives. [11b-11e] The reducti...

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“…The exchange reactions of com plex 3 with LiOH, PhCCNa, [(CH 3 ) 3 Si] 2 NK, C 5 H 5 Na, and C 5 Me 5 Na occur upon heating and afford the corre sponding derivatives [(dpp bian)Cr( OH)] 2 (4), [(dpp bian)Cr( CCPh)] 2 (5), (dpp bian)Cr[N(SiMe 3 ) 2 ](THF) (6), (dpp bian)Cr(C 5 H 5 ) (7), and (dpp bian)Cr(C 5 Me 5 ) (8) in high yields (Scheme 2).…”

Section: Methodsmentioning

confidence: 99%

Compounds of chromium, titanium, and zirconium with different reduced forms of acenaphthene-1,2-diimine

et al. 2014

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The reaction of Cr(CO) 6 with 1,2 bis[(2,6 diisopropylphenyl)imino]acenaphthene (1, dpp bian) affords a chromium complex with the neutral diimine ligand (dpp bian)Cr(CO) 4 (2). The exchange reactions of the compound [(dpp bian)Cr( Cl)(THF)] 2 (3) with LiOH, PhCCNa, [(CH 3 ) 3 Si] 2 NK, C 5 H 5 Na, and C 5 Me 5 Na give the corresponding radical anion derivatives, viz., [(dpp bian)Cr( OH)] 2 (4), [(dpp bian)Cr( CCPh)] 2 (5), (dpp bian)Cr[N(SiMe 3 ) 2 ] (THF) (6), (dpp bian)Cr(C 5 H 5 ) (7), and (dpp bian)Cr(C 5 Me 5 ) (8). The titanium and zirconi um complexes with the acenaphthene 1,2 diimine dianion, viz., (dpp bian) 2 Ti (9) and (dpp bian)Zr(Cl)Cp (10), were synthesized by the reactions of Na 2 (dpp bian) with TiCl 4 and CpZrCl 3 , respectively. All compounds were characterized by IR spectroscopy and elemental analysis. Diamagnetic derivatives 2, 9, and 10 were additionally studied by 1 H NMR spectro scopy. The structures of products 2, 4-8, and 10 were determined by X ray diffraction.Key words: diimine ligands, transition metals, molecular and electronic structures.1,2 Bis(arylimino)acenaphthenes were put in use as ligands in the coordination chemistry about 10 years ago. 1,2 Bis[(2,6 diisopropylphenyl)imino]acenaphthene (1, dpp bian) is the most commonly applied ligand of this class. Its distinguishing features are, first, the conforma tional rigidity of the diimine moiety, the nitrogen atoms of which are coordinated to the metal atom, and, second, the shielding of the coordination area by bulky substituents at the nitrogen atoms. This ensures the formation of mono meric metal complexes, in which the diimine ligand never acts as a bridging ligand. The absolutely unique property of the dpp bian ligand is its ability to be reversibly reduced by alkali metals to mono , di , tri , and tetraanions to form the salts [(dpp bian) n-M + n (Et 2 O) m ] (M = Li, Na; n = 1-4, m = 1-4). 1,2 Organometallic compounds, for example, Me 2 Mg 3 or EtMgBr, 4 can also reduce dpp bian. In the former case, the reaction is accompanied by the elimination of the methyl radical to give the oragno magnesium derivative with the dpp bian radical anion [(dpp bian)MgMe] 2 . The reaction of dpp bian with a Grignard reagent affords the addition product of the oragnomagnesium compound at one of the C=N bonds of the diimine, (dpp bian Et)MgBr(Et 2 O) 2 . Both reactions proceed through the one electron transfer to form the dpp bian radical anion, which recombines with the ethyl radi cal to give the final product.A series of compounds containing unusual metal-met al bonds, including derivatives of Group 13 metals having unique reactivity toward alkynes, of the general formula (dpp bian)M-M(dpp bian) (M = Ga, Al) were synthe sized using dpp bian as the ligand. 5-9 Like other diimines, dpp bian can stabilize low oxidation states, including di valent states of silicon and germanium. 10-12 The redox isomerization in the complex of a 4f element, viz., in the compound [(dpp bian)YbBr(DME)] 2 , 13 was accom plished for the first time using the dpp b...

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Addition of Alkynes to a Gallium Bis‐Amido Complex: Imitation of Transition‐Metal‐Based Catalytic Systems

Cited by 101 publications

References 72 publications

Gallium and Indium Compounds in Homogeneous Catalysis

Gallium and Indium Compounds in Homogeneous Catalysis

The Reduction of Sterically Hindered o‐Quinone and o‐Iminoquinone with Gallium and “GaI”

Compounds of chromium, titanium, and zirconium with different reduced forms of acenaphthene-1,2-diimine

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