In order to characterize the 2-electron 3-center hydride bridges in arachno-tetraborane, an experimental charge-density study was performed complemented with various theoretical calculations. The charge-density distribution and its topological properties were analyzed according to the "atoms in molecules" theory of Bader. The asymmetric bonding situation of the highly polarized hydride bridges is discussed in detail.
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http://dx.doi.org/10.1021/ic701924r | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Krupp-Chair for General and Inorganic Chemistry, Saarland University, 66123, Saarbrücken, Germany.
Unlike cyclopropanes, the analogous BC species (diboriranes) tend to adopt non-classical Hückel-aromatic structures with bridging moieties R between the boron atoms. The coordination of the thus generated cyclic 2e π-system to transition metals is completely unexplored. We here report that complexation of non-classical diboriranes cyclo-μ-RBDurCPh (R=H, SnMe; Dur=2,3,5,6-tetramethylphenyl) to Fe(CO) fragments allows for the carbonylative ring expansion of the BC ring to either four- or five-membered rings depending on the nature of the BRB 3-center-2-electron bond (3c2e): The H-bridged diborirane (R=H) initially reacts with Fe(CO) to the allylic π-complex with an agostic BH/Fe interaction.
View Article and Find Full Text PDFJ Org Chem
July 2024
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115, United States.
The chemistry of dicationic and tricationic 2-norbornyl cations has been studied. A series of -heterocyclic functionalized norborneol substrates were prepared and ionization of these compounds in superacid provided superelectrophilic species. These highly charged 2-norbornyl cations were found to react with arene nucleophiles in high yields and stereoselectivity.
View Article and Find Full Text PDFInorg Chem
April 2022
Laboratory of Catalysis, Polymerization, Processes and Materials, CP2M UMR 5128, CNRS, Université de Lyon, Institut de Chimie de Lyon, Université Lyon 1, ESCPE Lyon, 43 Bd du 11 Novembre 1918, F-69616 Villeurbanne, France.
We report an original alkane elimination approach, entailing the protonolysis of triisobutylaluminum by the acidic hydrides from Cp*IrH. This strategy allows access to a series of well-defined tri- and tetranuclear iridium aluminum polyhydride clusters, depending on the stoichiometry: [Cp*IrHAl(Bu)] (), [Cp*IrHAl(Bu)] (), [(Cp*IrH)Al(Bu)] (), and [(Cp*IrH)Al] (). Contrary to most transition-metal aluminohydride complexes, which can be considered as [AlH] aluminates and LnM moieties, the situation here is reversed: These complexes have original structures that are best described as [Cp*IrH] iridate units surrounding cationic Al(III) fragments.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2020
Tianjin Key Lab of Rare Earth Materials and Applications, State Key Laboratory of Elemento-Organic Chemistry, School of Materials Science and Engineering, Nankai University, Tianjin, 300350, China.
In this work, the largest heterometallic supertetrahedral clusters, [Zn Ge ] and [Cd Ge ] , were directly self-assembled through highly-charged [Ge ] units and transition metal cations, in which 3-center-2-electron σ bonding in Ge Zn or Ge Cd triangles plays a vital role in the stabilization of the whole structure. The cluster structures have an open framework with a large central cavity of diameter 4.6 Å for Zn and 5.
View Article and Find Full Text PDFInorg Chem
April 2020
Institute of Inorganic Chemistry of the Czech Academy of Sciences, Husinec-Řež, 250 68, Czech Republic.
The dimetallic boron hydride cluster, (PMePh)PtBH (-Pt), is known to reversibly sequester small molecules (e.g., O, CO, and SO) across its Pt-Pt cluster vector.
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