C‐H‐Aktivierung mit Komplexen der f‐Block‐Elemente

Arnold, Polly L.; McMullon, Max W.; Rieb, Julia; Kühn, Fritz E.

doi:10.1002/ange.201404613

Cited by 33 publications

(2 citation statements)

References 153 publications

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“…[ 33,34 ] For example, Francis Arnold found that enzymes could be re‐engineered for diagnostic use and was awarded the Nobel Prize in Chemistry in 2018 for her work in the directed evolution of enzymes. [ 35 ]…”

Section: Introductionmentioning

confidence: 99%

Development of Single Molecule Techniques for Sensing and Manipulation of CRISPR and Polymerase Enzymes

Chu

Romero

Taulbee

et al. 2023

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Clustered regularly interspaced short palindromic repeats (CRISPR) and polymerases are powerful enzymes and their diverse applications in genomics, proteomics, and transcriptomics have revolutionized the biotechnology industry today. CRISPR has been widely adopted for genomic editing applications and Polymerases can efficiently amplify genomic transcripts via polymerase chain reaction (PCR). Further investigations into these enzymes can reveal specific details about their mechanisms that greatly expand their use. Single‐molecule techniques are an effective way to probe enzymatic mechanisms because they may resolve intermediary conformations and states with greater detail than ensemble or bulk biosensing techniques. This review discusses various techniques for sensing and manipulation of single biomolecules that can help facilitate and expedite these discoveries. Each platform is categorized as optical, mechanical, or electronic. The methods, operating principles, outputs, and utility of each technique are briefly introduced, followed by a discussion of their applications to monitor and control CRISPR and Polymerases at the single molecule level, and closing with a brief overview of their limitations and future prospects.

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Section: Introductionmentioning

confidence: 99%

Development of Single Molecule Techniques for Sensing and Manipulation of CRISPR and Polymerase Enzymes

Chu

Romero

Taulbee

et al. 2023

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“…Simple,low-coordinate U III complexes have been recently reported to show arich reactivity with inert small molecules. [1] This reactivity is despite the fact that in the solid state, structural studies show close contacts between the metal and peripheral ligand Cand Hatoms that sometimes protect ap otential coordination site and sometimes simply block further reactions.F or example,h ydrocarbon solutions of [U(N'') 3 ](N'' = N(SiMe 3 ) 2 ) [2] (containing three UÀC SiMe3 close contacts,a verage distance = 3.047 ) reductively couple CO, [3] whereas those of [U{N(SiMe 2 Ph) 2 } 3 ]( containing three U À C ipsoPh close contacts,average distance = 3.093 ) [4] do not.…”

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Characterizing Pressure‐Induced Uranium CH Agostic Bonds

et al. 2015

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The diuranium(III) compound [UN'' 2 ] 2 (m-h 6 :h 6 -C 6 H 6 )( N '' = N(SiMe 3 ) 2 )h as been studied using variable, high-pressure single-crystal X-ray crystallography,and density functional theory .Inthis compound, the low-coordinate metal cations are coupled through p-and d-symmetric arene overlap and show close metalÀCH contacts with the flexible methyl CH groups of the sterically encumbered amido ligands.The metalmetal separation decreases with increasing pressure,b ut the most significant structural changes are to the close contacts between ligand CH bonds and the Ucenters.A lthough the interatomic distances are suggestive of agostic-type interactions between the Ua nd ligand peripheral CH groups,Q TAIM (quantum theory of atoms-in-molecules) computational analysis suggests that there is no such interaction at ambient pressure.H owever,Q TAIM and NBO analyses indicate that the interaction becomes agostic at 3.2 GPa.Simple,low-coordinate U III complexes have been recently reported to show arich reactivity with inert small molecules. [1] This reactivity is despite the fact that in the solid state, structural studies show close contacts between the metal and peripheral ligand Cand Hatoms that sometimes protect ap otential coordination site and sometimes simply block further reactions.F or example,h ydrocarbon solutions of [U(N'') 3 ](N'' = N(SiMe 3 ) 2 ) [2] (containing three UÀC SiMe3 close contacts,a verage distance = 3.047 ) reductively couple CO, [3] whereas those of [U{N(SiMe 2 Ph) 2 } 3 ]( containing three U À C ipsoPh close contacts,average distance = 3.093 ) [4] do not.Arguably the most useful homogeneous CÀHb ond functionalization reactions currently being developed for dblock metal catalysts rely on CH metallation of ab ound substrate. [5] Similarly,U complexes that show CH metallation [6] have been developed into catalysts for N-heterocycle coupling,f or example. [7] TheU III aryloxide [{(ArO) 3 tacn}U-(cC 6 H 12 )] (tacn = 1,4,7-triazacyclonane) shows an intermolecular CÀHc ontact to am olecule of cyclohexane solvent with aU À Cd istance of 3.864 (7) a nd an h 2 -CH interaction suggested by calculations. [8] More generally,a gostic interactions between uranium centers and ligand CH groups are often invoked from inspection of close metal-ligand contacts in X-ray structures. [9] No routine method exists for assessing the strength and influence of weak interactions to confirm ag enuine agostic interaction in paramagnets,w here traditional NMR spectral methods do not work [10] and neutron diffraction studies are not readily available. [11] Computationally,t he electron-density-basedq uantum theory of atoms-inmolecules (QTAIM), with its simple definition of achemical bond, has been successfully employed to identify agostic interactions. [12] Systems in which energetically competitive structures are related by subtle changes,such as agostic interactions,may be sensitive to external conditions such as pressure.H igh pressure has previously shown unconventional behavior in coordination compounds...

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Iridium‐Catalyzed Intramolecular C–H Silylation of Siloxane‐Tethered Arene and Hydrosilane: Facile and Catalytic Synthesis of Cyclic Siloxanes

et al. 2017

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Catalytic C–H silylation is an increasingly important topic in the field of organosilicon chemistry and homogenous catalysis as well as organic synthesis, but such syntheses and transformations are usually challenging and often incompatible with some functional groups. In this manuscript, a new type of silanol‐directed intramolecular dehydrogenative silylation under iridium catalysis has been developed. The described silylative cyclization has good functional group compatibility, providing a general and efficient route to unsymmetrical cyclic siloxanes with multiple potentially modifiable silicon atoms in high site‐selectivities. The resulting organosilicon compounds exhibit diverse synthetic applications owing to their unique structures.magnified image

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C‐H‐Aktivierung mit Komplexen der f‐Block‐Elemente

Cited by 33 publications

References 153 publications

Development of Single Molecule Techniques for Sensing and Manipulation of CRISPR and Polymerase Enzymes

Development of Single Molecule Techniques for Sensing and Manipulation of CRISPR and Polymerase Enzymes

Characterizing Pressure‐Induced Uranium CH Agostic Bonds

Iridium‐Catalyzed Intramolecular C–H Silylation of Siloxane‐Tethered Arene and Hydrosilane: Facile and Catalytic Synthesis of Cyclic Siloxanes

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