The reaction of cyclopentadienylidine, fluorenylidene and tetrachlorocyclopentadienylidene with alcohols. A laser flash photolysis study

Olson, David R.; Platz, Matthew S.

doi:10.1002/(sici)1099-1395(199611)9:11<759::aid-poc834>3.0.co;2-o

Cited by 17 publications

(2 citation statements)

References 27 publications

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“…The triplet state of FY (T-FY) is 2–3 kcal/mol more stable than its lowest singlet state (S-FY) . T-FY could be isolated in cryogenic matrices and characterized by EPR, IR, and UV–vis spectroscopy. − In solution, FY was characterized by time-resolved spectroscopy as a transient species with nanosecond lifetimes. − Here, we describe the STM characterization of FY stabilized on a Ag(111) surface.…”

Section: Introductionmentioning

confidence: 99%

Controlling Reactivity—Real-Space Imaging of a Surface Metal Carbene

et al. 2021

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Metal carbenes are key intermediates in a plethora of homogeneous and heterogeneous catalytic processes. However, despite their importance to heterogeneous catalysis, the influence of surface attachment on carbene reactivity has not yet been explored. Here, we reveal the interactions of fluorenylidene (FY), an archetypical aromatic carbene of extreme reactivity, with a Ag(111) surface. For the first time, the interaction of a highly reactive carbene with a metal surface could be studied by scanning tunneling microscopy (STM). FY chemisorbs on Ag(111) with an estimated desorption energy of 3 eV, forming a surface bound silver−carbene complex. The surface interaction leads to a switching of the electronic ground state of FY from triplet to singlet, and to controlled chemical reactivity. This atomistic understanding of the interplay between carbenes and metal surfaces opens the way for the development of novel classes of catalytic systems based on surface metal carbenes.

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Section: Introductionmentioning

confidence: 99%

Controlling Reactivity—Real-Space Imaging of a Surface Metal Carbene

et al. 2021

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“…Carbenes 5 and 6 had been previously isolated and spectroscopically characterized in inert gas matrices. − Several bimolecular reactions of these carbenes were studied under the conditions of matrix isolation − or by laser flash photolysis …”

Section: Introductionmentioning

confidence: 99%

Reactions of Cyclopentadienylidenes with CF₃I: Electron Bond Donation versus Halogen Bond Donation of the Iodine Atom

et al. 2018

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The interaction of cyclopentadienylidene and tetrachlorocyclopentadienylidene with the halogen bond donor CFI has been studied by matrix isolation spectroscopy. The carbenes were produced by photolysis of the corresponding diazo compounds, matrix-isolated in argon doped with 1% CFI at 3 K. Bimolecular reactions between the carbenes and CFI were induced by annealing these matrices to 25-30 K to allow for the diffusion of trapped species. Instead of classical halogen-bonded complexes, these carbenes form complexes in which the iodine atom is shared between the carbene center and the CF group. Photolysis of the complexes at 3 K yields radical pairs, which reversibly react back to the complexes when the matrices are warmed to 25-30 K.

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2‐Chloro‐Azaborolyl Anion: A Source of 1,2‐Azaborole Isosteric to Cyclopentadienylidene

Xie

Zhang

Cui

2014

Chemistry A European J

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Azaborolyl anions, the five-membered BN heterocycles, have attracted a considerable attention due to their aromaticity and isoelectronic relationship with ubiquitous cyclopentadienyl ligands. Besides their syntheses and applications in the preparation of metal complexes, the other aspects of their chemistry have been virtually unexplored. Reduction of the azabutadienyl chelate boron dichloride [ArNC(R)CHC(R)]BCl2 (2, Ar=2,6-Me2 C6 H3 , R=tBu) with two equivalents of potassium yielded the novel 2-chloro-azaborolyl anion [ArNC(R)CHC(R)BCl]K(thf) (3) as a stable product in good yield. Reaction of 3 with 1,3,4,5-tetramethylimidazol-2-ylidene (NHC) yielded the first NHC-azaborole adduct with the elimination of KCl. The salt elimination reaction was also observed in the reactions with H2 O and the organic azide ArN3 , leading to the formation of an oxo-bridged 3H-1,2-diazaborole and an intramolecular donor-stabilized iminoborane, demonstrating that 3 is a source of the unexplored 1,2-azaborole isosteric to cyclopentadienylidene.

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The reaction of cyclopentadienylidine, fluorenylidene and tetrachlorocyclopentadienylidene with alcohols. A laser flash photolysis study

Cited by 17 publications

References 27 publications

Controlling Reactivity—Real-Space Imaging of a Surface Metal Carbene

Controlling Reactivity—Real-Space Imaging of a Surface Metal Carbene

Reactions of Cyclopentadienylidenes with CF₃I: Electron Bond Donation versus Halogen Bond Donation of the Iodine Atom

2‐Chloro‐Azaborolyl Anion: A Source of 1,2‐Azaborole Isosteric to Cyclopentadienylidene

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The reaction of cyclopentadienylidine, fluorenylidene and tetrachlorocyclopentadienylidene with alcohols. A laser flash photolysis study

Cited by 17 publications

References 27 publications

Controlling Reactivity—Real-Space Imaging of a Surface Metal Carbene

Controlling Reactivity—Real-Space Imaging of a Surface Metal Carbene

Reactions of Cyclopentadienylidenes with CF3I: Electron Bond Donation versus Halogen Bond Donation of the Iodine Atom

2‐Chloro‐Azaborolyl Anion: A Source of 1,2‐Azaborole Isosteric to Cyclopentadienylidene

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Reactions of Cyclopentadienylidenes with CF₃I: Electron Bond Donation versus Halogen Bond Donation of the Iodine Atom