Different arene Cr(CO)(3) complexes were supported on a polystyrene isonitrile resin by photochemical-promoted replacement of a chromium carbonyl ligand by the NC group. The supported complexes proved to be stable and were successfully used for further transformations. In particular, the reactivity of dichlorobenzene complexes to different nucleophiles was investigated and found to be comparable with that of the parent Cr(CO)(3) complexes.
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http://dx.doi.org/10.1021/cc0340123 | DOI Listing |
Chemistry
January 2025
Politecnico di Milano, Department of Chemistry, Materials, Chemical Engineer., via Mancinelli 7, 20131, Milan, ITALY.
Molecular recognition mediated by s-hole interactions is enhanced as the electrostatic potential at the σ-hole becomes increasingly positive. Traditional methods to strengthen σ-hole donor ability of atoms such as halogens often involve covalent modifications, such as, introducing electron-withdrawing substituents (neutral or positively charged) or electrochemical oxidation. Metal coordination, a relatively underexplored approach, offers a promising alternative.
View Article and Find Full Text PDFAcc Chem Res
August 2024
Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, Hangzhou, Zhejiang 310030, China.
ConspectusLewis π acids, particularly high-valent transition metals with vacant orbitals, can coordinate with unsaturated compounds such as alkynes and alkenes by means of π-bonding. The coordination enhances the electrophilicity of the bound compounds, thereby facilitating reactions─such as nucleophilic addition─that take place at the ligated carbon-carbon multiple bonds. This activation phenomenon occurs at the ligand rather than at the metal atom, and it has been extensively utilized in the development of catalytic methods.
View Article and Find Full Text PDFJ Phys Chem A
May 2024
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Spectroscopic characterization of highly excited neutral transition-metal complexes is important for understanding the multifaceted reaction mechanisms between metals and ligands. In this work, the reactions of neutral chromium atoms with carbon monoxide were probed by size-specific infrared spectroscopy. Interestingly, Cr(CO) was found to have an unprecedented A septet excited state rather than the singlet ground state.
View Article and Find Full Text PDFDalton Trans
February 2024
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India.
In an effort to explore the coordination chemistry of the coordinative sulfur centers in -ruthenaborane [(Cp*Ru)(BH)(CSH)] (-1), we have thermolyzed -1 with group-6 metal carbonyls [M(CO)·THF] (M = Cr, Mo and W). The reaction of -1 with [Cr(CO)·THF] resulted in the formation of hetero-trimetallic triply bridging borylene [(Cp*Ru)(μ-CO)(μ-CHS-κS':κS''){Cr(CO)}(μ-BH)] (2), bridging boryl-borylene [(Cp*Ru)(μ-CO){(μ-BH(CHS)-κB:κS':κS'')}{Cr(CO)}(μ-BH)] (3), and sulfido bridged hetero-trimetallic complex [(Cp*Ru)(μ-CO){Cr(CO)}(μ-S)] (4). In 2, one side of RuCr-triangle features a μ-BH ligand while the other side is quadruply bridged by a methanedithiolato ligand in an unsymmetrical fashion.
View Article and Find Full Text PDFMolecules
November 2023
School of Chemistry, University College Dublin, Belfield, D04 V1W8 Dublin, Ireland.
The triple condensation of cyclopentanone or indanone to trindane (CH) or truxene (CH), respectively, provides convenient access to molecular skeletons on which major fragments of the prototypical fullerene C can be assembled. In particular, early approaches (both organic and organometallic) towards sumanene, as well as the final successful synthesis, are described. Organometallic derivatives of trindane have been prepared in which Cr(CO), Mo(CO), [Mn(CO)] or [(CH)Fe(CO)] are η-bonded to the central arene ring.
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