Single‐Electron‐Transfer Reactions of α‐Diimine dpp‐BIAN and Its Magnesium Complex (dpp‐BIAN)2–Mg2+(THF)3

Fedushkin, Igor L.; Makarov, V. M.; Rosenthal, Esther C. E.; Fukin, Georgy K.

doi:10.1002/ejic.200500860

Cited by 46 publications

(20 citation statements)

References 19 publications

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“…[14] Note that the reactions of [(dpp-bian)MgA C H T U N G T R E N N U N G (thf) 3 ] with R À X (Scheme 1) also proceed by addition across the metal-ligand 1,3-dipole and result in new carbon-carbon and magnesium-halide bonds. [15] In the context of activation of carbon-carbon multiple bonds in main-group-metal complexes, the recently reported addition of H 2 C=CH 2 to the metal-metal triple bond in ArSnSnAr is remarkable.…”

Section: Resultsmentioning

confidence: 98%

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

Fedushkin¹,

Nikipelov²,

Morozov³

et al. 2011

Chemistry A European J

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103

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Acetylene, phenylacetylene, and alkylbutynoates add reversibly to (dpp-bian)Ga-Ga(dpp-bian) (dpp-bian=1,2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene) to give addition products [dpp-bian(R(1)C=CR(2))]Ga-Ga[(R(2)C=CR(1))dpp-bian]. The alkyne adds across the Ga-N-C section, which results in new carbon-carbon and carbon-gallium bonds. The adducts were characterized by electron absorption, IR, and (1)H NMR spectroscopy and their molecular structures have been determined by single-crystal X-ray analysis. According to the X-ray data, a change in the coordination number of gallium from three [in (dpp-bian)Ga-Ga(dpp-bian)] to four (in the adducts) results in elongation of the metal-metal bond by approximately 0.13 Å. The adducts undergo a facile alkynes elimination at elevated temperatures. The equilibrium between [dpp-bian(PhC=CH)]Ga-Ga[(HC=CPh)dpp-bian] and [(dpp-bian)Ga-Ga(dpp-bian) + 2 PhC≡CH] in toluene solution was studied by (1)H NMR spectroscopy. The equilibrium constants at various temperatures (298≤T≤323 K) were determined, from which the thermodynamic parameters for the phenylacetylene elimination were calculated (ΔG°=2.4 kJ mol(-1), ΔH°=46.0 kJ mol(-1), ΔS°=146.0 J K(-1) mol(-1)). The reactivity of (dpp-bian)Ga-Ga(dpp-bian) towards alkynes permits use as a catalyst for carbon-nitrogen and carbon-carbon bond-forming reactions. The bisgallium complex was found to be a highly effective catalyst for the hydroamination of phenylacetylene with anilines. For instance, with [(dpp-bian)Ga-Ga(dpp-bian)] (2 mol%) in benzene more than 99% conversion of PhNH(2) and PhC≡CH into PhN=C(Ph)CH(3) was achieved in 16 h at 90 °C. Under similar conditions, the reaction of 1-aminoanthracene with PhC≡CH catalyzed by (dpp-bian)Ga-Ga(dpp-bian) formed a carbon-carbon bond to afford 1-amino-2-(1-phenylvinyl)anthracene in 99% yield.

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Section: Resultsmentioning

confidence: 98%

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

Fedushkin¹,

Nikipelov²,

Morozov³

et al. 2011

Chemistry A European J

Self Cite

103

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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%

“…1а)-Cr(1)-N(1) 98.15(4) O(1)-Cr(1)-N(2) 99.64(4) O(1а)-Cr(1)-N(2) 179.32(4) N(1)-Cr(1)-N(2) 82.46(4) Cr(1)-O(1)-Cr(1а)100.23(4) …”

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confidence: 97%

“…The replacement of CO groups by dpp bian in chromium hexacarbonyl requires the presence of an ex cess of the latter (2-4 moles of dpp bian per mole of Cr(CO) 6 ), the prolonged heating of the reaction mixture (20 h at 80 C), and the removal from time to time of carbon monoxide that formed. The synthesis under these conditions gave the compound (dpp bian)Cr(CO) 4 (2) in 52% yield (Scheme 1) as dark green crystals stable in air over a long period of time.…”

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confidence: 98%

“…Molecular structure of (dpp bian)Cr(CO)4 (2). Thermal ellipsoids are drawn at 30% probability level.…”

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confidence: 99%

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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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Miscellaneous Reactions

Hill¹

2019

Early Main Group Metal Catalysis

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Single‐Electron‐Transfer Reactions of α‐Diimine dpp‐BIAN and Its Magnesium Complex (dpp‐BIAN)^2–Mg²⁺(THF)₃

Cited by 46 publications

References 19 publications

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

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

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

Miscellaneous Reactions

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