Hydrido and chloro gallium and aluminium complexes with the tridentate bis(2-dimethylaminoethyl)amide ligand

Luo, Bing; Kucera, Benjamin E.; Gladfelter, Wayne L.

doi:10.1039/b607164c

Cited by 11 publications

(6 citation statements)

References 33 publications

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“…79 The compound H 2 Al[N(CH 2 CH 2 NMe 2 ) 2 ]AlH 3 provides a precedent for such an alane-amide adduct. 80 Unfortunately, many crystallization attempts failed to yield crystals. We rely on extensive NMR spectroscopic and density functional theory analysis to deduce possible structures of the complexes.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Iron(II) Complexes Containing Unsymmetrical P–N–P′ Pincer Ligands for the Catalytic Asymmetric Hydrogenation of Ketones and Imines

et al. 2014

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After their treatment with LiAlH4 and then alcohol, new iron dicarbonyl complexes mer-trans-[Fe(Br)(CO)2(P-CH═N-P')][BF4] (where P-CH═N-P' = R2PCH2CH═NCH2CH2PPh2 and R = Cy or iPr or P-CH═N-P' = (S,S)- Cy2PCH2CH═NCH(Me)CH(Ph)PPh2) are catalysts for the hydrogenation of ketones in THF solvent with added KOtBu at 50 °C and 5 atm H2. Complexes with R = Ph are not active. With the enantiopure complex, alcohols are produced with an enantiomeric excess of up to 85% (S) at TOF up to 2000 h(-1), TON of up to 5000, for a range of ketones. An activated imine is hydrogenated to the amine in 90% ee at a TOF 20 h(-1)and TON 99. This is a significant advance in asymmetric pressure hydrogenation using iron. The complexes are prepared in two steps: (1) a one-pot reaction of phosphonium dimers ([cyclo-(PR2CH2CH(OH)(-))2][Br]2), KOtBu, FeBr2, and Ph2PCH2CH2NH2 (or (S,S)-Ph2PCH(Ph)CH(Me)NH2 for the enantiopure complex) in THF under a CO atmosphere to produce the complexes cis- and trans-[Fe(Br)2(CO)(P-CH═N-P')]; (2) the reaction of these with AgBF4 under CO(g) to afford the dicarbonyl complexes in high yield (50-90%). NMR and DFT studies of the process of precatalyst activation show that the dicarbonyl complexes are converted first to hydride-aluminum hydride complexes where the imine of the P-CH═N-P' ligand is reduced to an amide [P-CH2N-P'](-) with aluminum hydrides still bound to the nitrogen. These hydride species react with alcohol to give monohydride amine iron compounds FeH(OR')(CO)(P-CH2NH-P'), R' = Me, CMe2Et as well as the iron(0) complex Fe(CO)2(P-CH2NH-P') under certain conditions.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Iron(II) Complexes Containing Unsymmetrical P–N–P′ Pincer Ligands for the Catalytic Asymmetric Hydrogenation of Ketones and Imines

et al. 2014

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“…As with carbon-supported aluminum hydride systems, a common reactivity pathway is the hydroalumination of organic π-bonds. Given the plethora of new N -donor aluminum hydride systems reported in the past two decades, ,− this section will aim to focus on the new bonding motifs and reactivity pathways uncovered in this area.…”

Section: Molecular Hydrides Of Group 13 Metals (Aluminum Gallium Indi...mentioning

confidence: 99%

Molecular Main Group Metal Hydrides

et al. 2021

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This review serves to document advances in the synthesis, versatile bonding, and reactivity of molecular main group metal hydrides within Groups 1, 2, and 12−16. Particular attention will be given to the emerging use of said hydrides in the rapidly expanding field of Main Group element-mediated catalysis. While this review is comprehensive in nature, focus will be given to research appearing in the open literature since 2001.

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“…[10,16,[18][19][20] Recently, we synthesized Ga, Al, and Zn precursors using ligands derived from HN(CH 2 CH 2 NMe 2 ) 2 . [21,22] Here we report the synthesis and structures of two monomeric Sr(tmhd) 2 adducts of this amine ligand, and the use of one of these, Sr(tmhd) 2 [HN(CH 2 CH 2 NMe 2 ) 2 ], in the CVD of strontium hafnium oxide films. Our interest in this mixed oxide system arose from the search for new, high-j dielectric materials for next-generation metal oxide semiconductor field effect transistors (MOSFETs).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structures of Bis(2‐dimethylaminoethyl)amine Adducts of Strontium Bis(2,2,6,6‐tetramethylheptane‐3,5‐dionate) and Their Use in the CVD of Cubic Strontium‐Doped Hafnium Dioxides

Luo¹,

Yu²,

Kucera³

et al. 2007

Chemical Vapor Deposition

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Monomeric, eight-coordinate Sr(tmhd) 2 [HN(CH 2 CH 2 NMe 2 ) 2 ](EtOH) (1), where tmhd is 2,2,6,6-tetramethylheptane-3,5-dionato, is synthesized from the reactions of HN(CH 2 CH 2 NMe 2 ) 2 , H-tmhd, and Sr(OEt) 2 (EtOH) 4 . Heating compound 1 at 130°C dissociates EtOH to form monomeric, seven-coordinate Sr(tmhd) 2 [HN(CH 2 CH 2 NMe 2 ) 2 ] (2). A combination of thermogravimetric analysis (TGA) and thermal stability tests establishes that compound 2 is stable at temperatures below 220°C. In a cold-wall, low-pressure CVD reactor, 2 is used as a liquid precursor at 115 to 175°C to deposit high-j, dielectric, strontium hafnium oxide films in combination with the use of Hf(O t Bu) 4 . The Sr/(Sr + Hf) atomic ratios of the films range from 0 to 0.83. X-ray diffraction (XRD) shows that films with low Sr doping, e.g., ≤ 0.15, exhibit a crystalline phase consistent with Sr-stabilized cubic hafnia, while films with higher Sr contents are amorphous. The dielectric constants of the films increase as the proportion of the cubic phase increases. A maximum value of 25 is obtained for the film with a Sr/(Sr + Hf) ratio of 0.07.

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Hydrido and chloro gallium and aluminium complexes with the tridentate bis(2-dimethylaminoethyl)amide ligand

Cited by 11 publications

References 33 publications

Iron(II) Complexes Containing Unsymmetrical P–N–P′ Pincer Ligands for the Catalytic Asymmetric Hydrogenation of Ketones and Imines

Iron(II) Complexes Containing Unsymmetrical P–N–P′ Pincer Ligands for the Catalytic Asymmetric Hydrogenation of Ketones and Imines

Molecular Main Group Metal Hydrides

Synthesis and Structures of Bis(2‐dimethylaminoethyl)amine Adducts of Strontium Bis(2,2,6,6‐tetramethylheptane‐3,5‐dionate) and Their Use in the CVD of Cubic Strontium‐Doped Hafnium Dioxides

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