Two structural transitions in covalent aluminum hydride AlH3 were characterized at high pressure. A metallic phase stable above 100 GPa is found to have a remarkably simple cubic structure with shortest first-neighbor H-H distances ever measured except in H2 molecule. Although the high-pressure phase is predicted to be superconductive, this was not observed experimentally down to 4 K over the pressure range 120-164 GPa. The results indicate that the superconducting behavior may be more complex than anticipated.
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http://dx.doi.org/10.1103/PhysRevLett.100.045504 | DOI Listing |
Adv Sci (Weinh)
January 2025
Materials and Structures Laboratory, Institute of Integrated Research, Institute of Science Tokyo, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan.
Achieving a substantial increase in the ammonia productivity of the Haber-Bosch (HB) process at low temperatures has been a significant challenge for over 100 years. However, the iron catalyst designed over 100 years ago remains at the forefront of this process because it is difficult to exceed the industrial iron catalyst in terms of the ammonia synthesis rate/catalyst volume that determines ammonia productivity in a reactor. Here, a new catalyst with an inverse structure of a supported metal catalyst that consists of metallic iron particles loaded with an aluminum hydride species is reported.
View Article and Find Full Text PDFChemistry
January 2025
University of Oxford, Inorganic Chemistry Laboratory, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
Combining experiment and theory, the mechanisms of H2 activation by the potassium-bridged aluminyl dimer K2[Al(NON)]2 (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tertbutyl-9,9-dimethylxanthene) and its monomeric K+-sequestered counterpart have been investigated. These systems show diverging reactivity towards the activation of dihydrogen, with the dimeric species undergoing formal oxidative addition of H2 at each Al centre under ambient conditions, and the monomer proving to be inert to dihydrogen addition. Noting that this K+ dependence is inconsistent with classical models of single-centre reactivity for carbene-like Al(I) species, we rationalize these observations instead by a cooperative frustrated Lewis pair (FLP)-type mechanism (for the dimer) in which the aluminium centre acts as the Lewis base and the K+ centres as Lewis acids.
View Article and Find Full Text PDFNat Commun
January 2025
State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China.
Chiral binaphthols (BINOL)-metal combinations serve as powerful catalysts in asymmetric synthesis. Their chiral induction mode, however, typically relies on multifarious non-covalent interactions between the substrate and the BINOL ligand. In this work, we demonstrate that the chiral-at-metal stereoinduction mode could serve as an alternative mechanism for BINOL-metal catalysis, based on mechanistic studies of BINOL-aluminum-catalyzed asymmetric hydroboration of heteroaryl ketones.
View Article and Find Full Text PDFOrg Lett
November 2024
Department of Chemistry, University of Georgia, Athens, Georgia 30602, United States.
We describe a practical method for the synthesis of various substituted -alkyl-1,3-dihydro-2,1-benzisoxazoles and their 2,1-benzisoxazolone precursors starting from readily available methyl 2-nitrobenzoates. The method entails partial nitro reduction with hydrazine and rhodium on carbon to give the hydroxylamines, followed by base-mediated cyclization to give the corresponding benzisoxazol-3(1)-ones. Subsequent alkylation is conducted under basic conditions and is followed by reduction to the target 1,3-dihydrobenzisoxazoles, achieved with lithium aluminum hydride in the presence of trimethylsilyl chloride.
View Article and Find Full Text PDFChemistryOpen
October 2024
CNRS, ICMMO, CP3A Organic Synthesis Group, Université Paris-Saclay, 17 Avenue des Sciences, 91400, Orsay, France.
N-substituted derivatives of anti-(2R,3S)-1,3-diamino-4-phenylbutan-2-ol are important building blocks for the synthesis of therapeutically important molecules. We describe a simple protocol that allows transformation of N,N-dibenzyl-L-phenylalaninal into such compounds in only two steps. The first step is a fully stereoselective three-component MAC (Masked Acyl Cyanide) oxyhomologation reaction implicating different amines to give a panel of ten N,N-dibenzyl-O-tert-butyldimethylsilyl-protected anti-(2S,3S)-allophenylnorstatin amides.
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