The potential energy surfaces of 15 tetrahedral p-block element hydrides were screened on the multireference level. It was addressed whether stereoinversion competes against other reactions, such as reductive H-elimination or hydride loss, and if so, along which pathway the stereomutation occurs. Importantly, stereoinversion transition structures for the ammonium cation (C) and the tetrahydridoborate anion (C) were identified for the first time. Revisiting methane's C symmetric inversion transition structure with the mHEAT+ protocol revealed an activation enthalpy for stereoinversion, in contrast to all earlier studies, which is 5 kJ mol below the C-H bond dissociation enthalpy. Square planar structures were identified lowest in energy only for the inversion of AlH , but a novel stepwise C-inversion was discovered for SiH or PH . Overall, the present contribution delineates essentials of the potential energy surfaces of p-block element hydrides, while structure-energy relations offer design principles for the synthetically emerging field of structurally constrained compounds.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1063/5.0090267 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Electrochemical reduction of CO on pure and doped CuO(111).
J Colloid Interface Sci
December 2024
Institute of Applied Physics and Materials Engineering, University of Macau, Macao SAR 999708, PR China; Department of Physics and Chemistry, Faculty of Science and Technology, University of Macau, Macao SAR 999708, PR China. Electronic address:
CuO has been demonstrated to be effective for converting CO into value-added products. However, the mechanism of the carbon dioxide reduction (COR) on the most stable surface, CuO(111), is still under debate. Additionally, how to improve its activity and selectivity is a challenging issue too.
View Article and Find Full Text PDFActivation of CO, CS, and COS by α-Diimine-Stabilized Gallylenes.
Chemistry
November 2024
Key Laboratory of Medicinal Molecule Science and Pharmaceutics Engineering, Ministry of Industry and Information Technology, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 100081, China.
Several gallylenes [LGaM(THF)] stabilized by an α-diimine ligand (L=[(2,6-iPrCH)NC(Ph)] ; M=Li, n=3, 3-Li; M=Na, n=4, 3-Na; M=K, n=1, 3-K) were prepared, which display diverse reactivities toward carbon dioxide and its sulfurized analogues. The reaction of 3 with CO yielded a trimeric carbonate complex [{LGa(CO)}{μ-K(THF)}] (4) and a dinuclear oxo-carbonate complex [K(THF)][LGa(μ-CO)(μ-O)GaL] (5) in one pot through reductive disproportionation of CO. For CS, two ethenetetrathiolate gallium complexes, [M(Solv)][LGa(μ-CS)GaL] (M=Na, Solv=THF, 6; M=K, Solv=DME, 7), were obtained via reductive coupling of CS.
View Article and Find Full Text PDFStructurally constraining p-block elements has become a powerful strategy for bond activation chemistry with main group compounds. Traditionally, this approach focuses on mononuclear centers, yet applying structural constraints to systems with element-element bonds remains underexplored. In this study, we introduce a cation featuring a structural constraint-elongated P-P bond that spontaneously adds to unactivated alkynes, alkenes, aldehydes, and ketones.
View Article and Find Full Text PDFRelativistic Prolapse-Free Gaussian Basis Sets of Double- and Triple-ζ Quality for - and -Block Elements: (aug-)RPF-2Z and (aug-)RPF-3Z.
J Chem Theory Comput
November 2024
Department of Chemistry and Molecular Physics, São Carlos Institute of Chemistry, University of São Paulo, C.P. 780, São Carlos, São Paulo 13560-970, Brazil.
This study presents two new relativistic Gaussian basis sets without variational prolapse of double- and triple-ζ quality, RPF-2Z and RPF-3Z, along with augmented versions including additional diffuse functions, aug-RPF-2Z and aug-RPF-3Z, which are available for all and block elements from Hydrogen to Oganesson. The exponents of the Correlation/Polarization (C/P) functions are obtained from a polynomial version of the generator coordinate Dirac-Fock method (p-GCDF). The choice of C/P functions was guided by multireference configuration interaction calculations with single and double excitations (MR-CISD) based on a valence active space.
View Article and Find Full Text PDFThe ring-opening polymerization (ROP) of l-lactide (l-LA) is the main method for synthesizing poly(l-lactide) (PLLA), in which choosing the catalyst is one of the most important parameters. In this work, we focused on the systematic study of catalysts based on p-block elements from period 5, such as indium(iii), tin(ii), tin(iv) and antimony(iii) acetates, which displayed contrasting performances influenced by the oxidation state of the metal center. Analysis of the obtained oligomers by different techniques, including nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), polarized optical microscopy (POM) and matrix-assisted laser desorption ionization-time-of-flight (MALDI-TOF), revealed the selectivity of each catalyst toward the ROP of l-LA.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!