Alkali Metal (Li, Na, K, Rb, Cs) Mediation in Magnesium Hexamethyldisilazide [Mg(HMDS)<sub>2</sub>] Catalysed Transfer Hydrogenation of Alkenes

Gentner, Thomas Xaver; Kennedy, Alan R.; Hevia, Eva; Mulvey, Robert E.

doi:10.1002/cctc.202100218

Cited by 31 publications

(40 citation statements)

References 55 publications

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“…1 H NMR (600 MHz, C 6 D 5 Br, 298 K) δ 8.00 (d, 3 J HH = 7.5 Hz, 4H, ArH (pyrene)), 7.90 (s, 4H, ArH (pyrene)), 7.85 (t, 3 J HH = 7.5 Hz, 2H, ArH (pyrene)), 7.12-7.08 (m, 6H, ArH), 4.82 (s, 1H, CCHC), 2.73 (hept, 3 J HH = 6.8 Hz, 4H, CHMe 2 ), 1.63 (s, 6H, CH 3 ), 1.08 (d, 3 J HH = 6.8 Hz, 12H, CHCH 3 ), 1.00 (d, 3 J HH = 6.8 Hz, 12H, CHCH 3 ) ppm. 13 3 J FF = 21 Hz, 4F, p-CF), À 163.9 (s, 8F, m-CF) ppm. 11 B{ 1 H} NMR (128 MHz, C 6 D 5 Br, 298 K) δ À 16.1 (s, B(C 6 F 5 ) 4 ) ppm.…”

Section: Experimental Section General Experimental Proceduresmentioning

confidence: 99%

“…1 H NMR (600 MHz, C 6 D 6 , 298 K) δ 7.93 (d, 3 J HH = 7.5 Hz, 4H, ArH (pyrene)), 7.83 (s, 4H, ArH (pyrene)), 7.76 (t, 3 J HH = 7.5 Hz, 2H, ArH (pyrene)), 7.08-7.03 (m, 6H, ArH), 4.48 (s, 1H, CCHC), 2.41 (hept, 3 J HH = 6.8 Hz, 4H, CHMe 2 ), 1.43 (s, 6H, CH 3 ), 1.06 (d, 3 J HH = 6.8 Hz, 12H, CHCH 3 ), 1.04 (d, 3 J HH = 6.8 Hz, 12H, CHCH 3 ) ppm. 13 À ] (0.1880 g, 0.1710 mmol) and SrN" 2 (0.0768 g, 0.1880 mmol, 1.1 eq.) were dissolved in chlorobenzene (3 mL).…”

Section: Experimental Section General Experimental Proceduresmentioning

confidence: 99%

“…1 H NMR (600 MHz, C 6 D 5 Br, 298 K) δ 8.00 (d, 3 J HH = 7.5 Hz, 4H, ArH (pyrene)), 7.90 (s, 4H, ArH (pyrene)), 7.85 (t, 3 J HH = 6.9 Hz, 4H, CHMe 2 ), 1.40 (s, 6H, CH 3 ), 1.06 (d, 3 J HH = 6.9 Hz, 12H, CHCH 3 ), 1.00 (d, 3 J HH = 6.9 Hz, 12H, CHCH 3 ) ppm. 13 ] was synthesized by an optimized literature procedure. [42,50] [(BDI)H 2 + ][B(C 6 F 5 ) 4 À ] (0.2160 g, 0.1830 mmol) and CaN" 2 (0.0780 g, 0.2010 mmol, 1.1 eq.)…”

Section: Experimental Section General Experimental Proceduresmentioning

confidence: 99%

“…1 3 J HH = 7.5 Hz, 4H, ArH (pyrene)), 7.83 (s, 4H, ArH (pyrene)), 7.76 (t, 3 J HH = 7.5 Hz, 2H, ArH (pyrene)), 7.08-6.98 (m, 6H, ArH), 4.68 (s, 1H, CCHC), 2.51 (hept, 3 J HH = 6.9 Hz, 4H, CHMe 2 ), 1.38 (s, 6H, CCH 3 ), 1.00 (d, 3 J HH = 6.9 Hz, 12H, CHCH 3 ), 0.93 (d, 3 J HH = 6.9 Hz, 12H, CHCH 3 ) ppm. 13 À ] (0.0458 g, 0.0497 mmol) were dissolved in chlorobenzene (0.3 mL) and stirred until the solution became almost colorless (1 min). After addition of pyrene (0.0300 g, 0.1490 mmol) and filtration, the reaction mixture was left at room temperature overnight.…”

Section: Experimental Section General Experimental Proceduresmentioning

confidence: 99%

“…[1][2][3] The field lately witnessed major breakthroughs especially in alkene and arene hydrogenation or functionalization. [4][5][6][7][8][9][10][11][12][13] Intermediate metal-alkene or arene πcomplexes play a superordinate role in substrate activation. For example, Ca-alkene interactions have been found crucial for successful catalytic alkene hydroamination.…”

Section: Introductionmentioning

confidence: 99%

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Lewis Acidic Cationic Strontium and Barium Complexes

et al. 2021

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Lewis acidic (BDI)Ae + cations of the heavier metals Sr and Ba, which are not stabilized by polar solvents, have been obtained by double deprotonation of ( BDI)H 2 + with either SrN'' 2 or BaN'' 2 ; BDI = HC[C(Me)N(DIPP)] 2 , DIPP = 2,6-diisopropylphenyl, Ae = alkaline earth, N'' = N(SiMe 3 ) 2 . Due to clathrate formation [(BDI)Ae + ][B(C 6 F 5 ) 4 À ] could not be crystallized, but pyrene addition gave crystalline [(BDI)Ae + • pyrene][B(C 6 F 5 ) 4 À ] which was structurally characterized for Ae = Mg, Ca, Sr, Ba. (R 2 N)Ae + cations of the heavier metals Sr and Ba were obtained by reaction of Ae(NR 2 ) 2 with [Ph 3 C + ][B(C 6 F 5 ) 4 À ] or [PhNMe 2 H + ] [B(C 6 F 5 ) 4 À ]. Following complexes were structurally characterized: [N''Ba + • (tol) 2 ][B(C 6 F 5 ) 4 À ], [N*Sr + • PhNMe 2 ][B(C 6 F 5 ) 4 À ], [N*Ba + • tol] [B(C 6 F 5 ) 4 À ] and [N*Ba + • C 6 H 6 ][B(C 6 F 5 ) 4 À ]; tol = toluene and N* = N(SiiPr 3 ) 2 . DFT calculations show that Sr•••PhNMe 2 coordination is preferred over Sr•••toluene bonding. The (R 2 N)Ae + cations can be used as Brønsted bases (reaction with (BDI)H gave (BDI)Ae + ) and may be useful precursors for a variety of Lewis base-free RAe + cations. DFT calculations, limited to monomeric model systems including B(C 6 F 5 ) 4 À(ωB97XD/def2tzvpp//ωB97XD/ def2svp), show that there is negligible electron transfer from the pyrene or toluene ligands to the Ae 2 + cation. Electrostatic attraction originates from charge-induced polarization of the p-electron density in the toluene and pyrene ligands.

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Section: Experimental Section General Experimental Proceduresmentioning

confidence: 99%

Section: Experimental Section General Experimental Proceduresmentioning

confidence: 99%

Section: Experimental Section General Experimental Proceduresmentioning

confidence: 99%

Section: Experimental Section General Experimental Proceduresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Lewis Acidic Cationic Strontium and Barium Complexes

et al. 2021

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Anionic Magnesium and Calcium Hydrides: Transforming CO into Unsaturated Disilyl Ethers

et al. 2022

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The synthesis, characterisation and reactivity of two isostructural anionic magnesium and calcium complexes is reported. By X‐ray and neutron diffraction techniques, the anionic hydrides are shown to exist as dimers, held together by a range of interactions between the two anions and two bridging potassium cations. Unlike the vast proportion of previously reported dimeric group 2 hydrides, which have hydrides that bridge two group 2 centres, here the hydrides are shown to be “terminal”, but stabilised by interactions with the potassium cations. Both anionic hydrides were found to insert and couple CO under mild reaction conditions to give the corresponding group 2 cis‐ethenediolate complexes. These cis‐ethenediolate complexes were found to undergo salt elimination reactions with silyl chlorides, allowing access to small unsaturated disilyl ethers with a high percentage of their mass originating from the C1 source CO.

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Alkali‐Metal‐Alkoxide Powered Zincation of Fluoroarenes Employing Zinc Bis‐Amide Zn(TMP)₂

Judge

Hevia

2023

Angewandte Chemie

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Reminiscent of Lochmann‐Schlosser superbase recipes, the addition of two molar equivalents of KOtBu to Zn(TMP)2 (TMP=2,2,6,6‐tetramethylpiperidide) transforms this mild zinc bis‐amide base to a powerful metalating agent able to perform facile regioselective zincation of a wide range of sensitive fluoroarenes. Structural authentication of the intermediates post Zn−H exchange demonstrates activation of both TMP groups to form a range of higher order bis‐aryl potassium zincates, isolable as solids and further functionalized in electrophilic interception reactions. Studies assessing the role of KOtBu reveal that the first equivalent undergoes co‐complexation with Zn(TMP)2, enabling kinetic activation of the amide groups; whereas the second equivalent stabilizes the metalated intermediate preventing ligand redistribution. Showcasing its metalating power, this bimetallic KOtBu/Zn(TMP)2 partnership, can effect zincation of toluene and benzene at room temperature.

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Alkali Metal (Li, Na, K, Rb, Cs) Mediation in Magnesium Hexamethyldisilazide [Mg(HMDS)₂] Catalysed Transfer Hydrogenation of Alkenes

Abstract: This publication is part of a joint Special Collection with EurJIC on "Main Group Catalysis". Please check the ChemCatChem homepage for more articles in the collection.

Cited by 31 publications

References 55 publications

Lewis Acidic Cationic Strontium and Barium Complexes

Lewis Acidic Cationic Strontium and Barium Complexes

Anionic Magnesium and Calcium Hydrides: Transforming CO into Unsaturated Disilyl Ethers

Alkali‐Metal‐Alkoxide Powered Zincation of Fluoroarenes Employing Zinc Bis‐Amide Zn(TMP)₂

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Alkali Metal (Li, Na, K, Rb, Cs) Mediation in Magnesium Hexamethyldisilazide [Mg(HMDS)2] Catalysed Transfer Hydrogenation of Alkenes

Abstract: This publication is part of a joint Special Collection with EurJIC on "Main Group Catalysis". Please check the ChemCatChem homepage for more articles in the collection.

Cited by 31 publications

References 55 publications

Lewis Acidic Cationic Strontium and Barium Complexes

Lewis Acidic Cationic Strontium and Barium Complexes

Anionic Magnesium and Calcium Hydrides: Transforming CO into Unsaturated Disilyl Ethers

Alkali‐Metal‐Alkoxide Powered Zincation of Fluoroarenes Employing Zinc Bis‐Amide Zn(TMP)2

Contact Info

Product

Resources

About

Alkali Metal (Li, Na, K, Rb, Cs) Mediation in Magnesium Hexamethyldisilazide [Mg(HMDS)₂] Catalysed Transfer Hydrogenation of Alkenes

Alkali‐Metal‐Alkoxide Powered Zincation of Fluoroarenes Employing Zinc Bis‐Amide Zn(TMP)₂