In crystal structures of the molybdenum complexes [(1,2,4-C5H2(t)Bu3)Mo(PMe3)2H3] (Cp(t)Bu3) and [(C5H(i)Pr4)Mo(PMe3)2H3] (Cp(i)Pr4), the Mo-bound hydrogen positions were resolved for Cp(t)Bu3, but not for Cp(i)Pr4. NMR experiments revealed the existence of an unknown mechanism for hydrogen atom exchange in these molecules, which can be "frozen out" for Cp(t)Bu3 but not for Cp(i)Pr4. Density functional theory calculations of the most stable conformations for both complexes in the gas phase and in a continuum solvent model indicate that the H's of the Cp(i)Pr4 complex are unresloved because of their disorder, which does not occur for Cp(t)Bu3. A corresponding examination of alternative rearrangement pathways shows that the rearrangements of the H's could occur by two mechanisms: parallel to the cyclopentadienyl (Cp) ring in a single step and perpendicular to the Cp ring in two steps. The parallel pathway is preferred for both molecules, but it has a lower energy barrier for Cp(i)Pr4 than for Cp(t)Bu3.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.inorgchem.5b00693 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
1.5D Chiral Perovskites Mediated by Hydrogen-Bonding Network with Remarkable Spin-Polarized Property.
Angew Chem Int Ed Engl
January 2025
Tianjin University, School of Chemical Engineering and Technology, Yaguan Road #135, Jinnan District, Tianjin 300354, P. R. China, CHINA.
In this study, we developed new chiral hybrid perovskites, (R/S-MBA)(GA)PbI4, by incorporating achiral guanidinium (GA+) and chiral R/S-methylbenzylammonium (R/S-MBA+) into the perovskite framework. The resulting materials possess a distinctive structural configuration, positioned between 1D and 2D perovskites, which we describe as 1.5D.
View Article and Find Full Text PDFSynergistic Effects of NO/HS Gases on Antibacterial, Anti-inflammatory, and Analgesic Properties in Oral Ulcers Using a Gas-Releasing Nanoplatform.
Acta Biomater
January 2025
School and Hospital of Stomatology, Wenzhou Medical University, Wenzhou, 325027, P. R. China. Electronic address:
Article Synopsis
- Oral mucosal wounds are susceptible to inflammation and complications due to exposure to microorganisms, which can hinder daily activities and diminish quality of life.
- A novel therapeutic nanoplatform, DATS@Arg-EA-SA, has been developed to target these wounds by combining guanidinated dendritic peptides with diallyl trisulfide (DATS), providing both antimicrobial and anti-inflammatory effects.
- This nanoplatform effectively eliminates various bacteria, including drug-resistant strains like MRSA, and enhances healing by promoting the transition of inflammatory cells and alleviating pain, making it a promising solution for oral wound treatment.
Fe(III)-Catalyzed Ring Expansion of Cyclopropenone from Olefins via Radicals to Access Pyrone and Indanone Derivatives.
Org Lett
January 2025
Department of Chemistry, Xihua University, Chengdu 610039, P. R. China.
A novel approach for the synthesis of pyrone and indanone derivatives utilizing Fe(III)-catalyzed reductive radical ring expansion of olefins and cyclopropenone has been proposed. The preliminary mechanism study shows that the alkyl radical is formed by hydrogen atom transfer, which can open the tension ring and then generate the intermediate. There are two paths for the intermediate: when there is a hydroxyl group at the β-position of the olefin, the reaction produces pyrones, and otherwise 1-indanone is generated.
View Article and Find Full Text PDFSelf-Sustained Biophotocatalytic Nano-Organelle Reactors with Programmable DNA Switches for Combating Tumor Metastasis.
Adv Mater
January 2025
Key Laboratory of Marine Drugs, Chinese Ministry of Education, School of Medicine and Pharmacy, Ocean University of China, Qingdao, 266003, P. R. China.
Metastasis, the leading cause of mortality in cancer patients, presents challenges for conventional photodynamic therapy (PDT) due to its reliance on localized light and oxygen application to tumors. To overcome these limitations, a self-sustained organelle-mimicking nanoreactor is developed here with programmable DNA switches that enables bio-chem-photocatalytic cascade-driven starvation-photodynamic synergistic therapy against tumor metastasis. Emulating the compartmentalization and positional assembly strategies found in living cells, this nano-organelle reactor allows quantitative co-compartmentalization of multiple functional modules for the designed self-illuminating chemiexcited PDT system.
View Article and Find Full Text PDFResonant and Non-Resonant Impurity States Related to GaAs/AlGaAs Quantum Well Sub-Bands.
Materials (Basel)
December 2024
Centro de Investigación en Ciencias-IICBA, Universidad Autónoma del Estado de Morelos, Cuernavaca 62209, Mexico.
The energy positions and wave function shapes of the ground and excited states of impurities, including resonance states, are studied using the expansion of the impurity wave function in basis functions. The structures under study are rectangular GaAs/AlGaAs quantum wells with four different widths. In all cases, the impurity binding energy (relative to the corresponding sub-band) has a maximum at or near the center of the quantum well, decreases as the heterointerface is approached, and apparently has a limit of 0 if the impurity moves deeper into the barrier.
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!