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In this work, a 2D covalent organometallic nanosheet (COMS) was designed and successfully synthesized through the one-step conjunction of a terpyridine-metal-terpyridine (TMT) sandwich coordinate motif with borate ester covalent heterocyclic (BO) linkage the condensation of boronic acid. The obtained 2D COMS with a cobalt coordination center (2D COMS-Co) showed promising p-type semiconducting properties.
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http://dx.doi.org/10.1039/c9ra05806k | DOI Listing |
Phys Chem Chem Phys
September 2025
Computational Inorganic Chemistry Group, Department of Chemistry, Indian Institute of Technology Hyderabad, Kandi, Sangareddy, Telangana 502284, India.
Over the past few years, alkali and alkaline earth metals have emerged as alternative catalysts to transition metal organometallics to catalyze the hydroboration of unsaturated compounds. A highly selective and cost-effective lithium-catalyzed method for the synthesis of an organoborane has been established based on the addition of a B-H bond to an unsaturated bond (polarized or unpolarized) using pinacolborane (HBPin). In the present work, the neosilyllithium-catalyzed hydroboration of nitriles, aldehydes, and esters has been investigated using high-level DLPNO-CCSD(T) calculations to unravel the mechanistic pathways and substrate-dependent reactivity.
View Article and Find Full Text PDFChem Sci
August 2025
P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania 231 S. 34th St. Philadelphia PA 19104 USA
Organometallic cerium(iv) complexes have been challenging to isolate and characterize due to the strongly oxidizing nature of the cerium(iv) cation. Herein, we report two cerium(iv) alkynyl complexes, [Ce(TriNOx)(C[triple bond, length as m-dash]C-SiMe)] (1-Ce) and [Ce(TriNOx)(C[triple bond, length as m-dash]C-Ph)] (1-Ce) (TriNOx = (2--butylhydroxylaminato)benzylamine), that include terminal alkyne moieties. The isostructural thorium analogue [Th(TriNOx)(C[triple bond, length as m-dash]C-SiMe)] (1-Th) was also synthesized and compared with 1-Ce in bond distance, C-NMR spectra, vibrational spectra and electronic structure.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
School of Energy and Environment, Southeast University, Nanjing, 211189, China.
Two-dimensional covalent organic frameworks (2D COFs) have emerged as promising photocatalysts due to their high surface areas and precisely tunable physicochemical properties. However, it remains a significant challenge to precisely control over interlayer stacking configurations in 2D COFs, which critically influence charge carrier transport and consequently determine catalytic efficiency. In this study, we demonstrate a solvent-driven strategy to precisely regulate the interlayer stacking configurations of metal-incorporated 2D COFs, successfully achieving both AA eclipsed (COF-TD-AA) and ABC staggered (COF-TD-ABC) configurations.
View Article and Find Full Text PDFOrganometallics
August 2025
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, United States.
We report the synthesis of Rh-Sb complexes using high valent Sb ligands, QSbCl (, Q = 8-quinolinyl) and QSbF (), from the low valent Rh precursor [(CO)Rh-(μ-Cl)] to afford the complexes [(κ-QSbCl)-Rh-(CO)-Cl]-[(CO)RhCl] () and (κ-QSbF)-Rh-(CO)Cl (), respectively. The reaction of with [(CO)Rh-(μ-Cl)] results in the transfer of chloride from Sb to Rh to give the ion pair with a Rh-Sb bond for the cation that, according to computational analysis, has some covalent character. Replacing Sb-Cl with Sb-F bonds (, compound ) inhibited halide transfer and allowed formation of with a Rh→Sb interaction that has more Z-type character than the Rh-Sb bond for complex .
View Article and Find Full Text PDFOrganometallics
August 2025
The University of Iowa, Department of Chemistry, E331 Chemistry Building, Iowa City, Iowa 52242, United States.
Ligand K-edge X-ray absorption spectroscopy (XAS), a technique that can measure variations in covalent metal-ligand bonding, has rarely been used to assess covalency in complexes containing metal-boron bonds. Here we describe ligand K-edge XAS and TDDFT studies of the Ni dicarbollide complex Ni-(CBH) () and the Ni-free salt (HNMe)-(CBH) (). The XAS spectrum for reveals a pre-edge feature indicative of covalent Ni-B bonding, which is corroborated by time-dependent density functional theory (TDDFT) calculations and comparative analysis to and inner-shell electron energy loss spectroscopy (ISEELS) collected on the same Ni complex.
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