Carbenes in matrices: Spectroscopy, structure, and photochemical behavior

Maier, Günther; Reisenauer, Hans Peter

doi:10.1016/s1079-350x(01)80005-8

Cited by 18 publications

(8 citation statements)

References 258 publications

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“…In combination with our work on monocyanocarbene (1), [9] and with regard to the still existing inconsistencies in the experimental and theoretical studies on T-5, we decided to study 5 in more detail. The results, already touched upon in a review article on ''Carbenes in Matrices'', [16] are presented in full here.…”

Section: Introductionmentioning

confidence: 85%

Dicyanocarbene and Its Isomers: A Matrix Spectroscopic Study

2003

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Irradiation of matrix‐isolated dicyanodiazomethane (4) with 254 nm‐light leads to the dicyanocarbene 5, which, upon further photoexcitation, undergoes successive isomerizations until a photoequilibrium between the five C3N2 isomers dicyanocarbene (T‐5), cyanoisocyanocarbene (T‐6), 3‐cyano‐2H‐azirenylidene (S‐7), 3‐isocyano‐2H‐azirenylidene (S‐8), and diisocyanocarbene (S‐9) is reached. The preferential formation of a specific member of this group can be achieved by changing the wavelength of the irradiating light. The structural elucidation of the unknown compounds 6−9 is based on a comparison of their calculated and experimental IR spectra. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Section: Introductionmentioning

confidence: 85%

Dicyanocarbene and Its Isomers: A Matrix Spectroscopic Study

2003

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“…While stable NHCs could be deposited on single crystalline metal surfaces and characterized by microscopic techniques in real space, ,,,, a similar characterization of highly reactive electrophilic carbenes could not be achieved, so far. Due to their extreme reactivity, the spectroscopic characterization of electrophilic carbenes requires either time-resolved or matrix isolation techniques. , Since many NHCs are stable at room temperature, they can be directly deposited on metal surfaces. In a study comparing the self-assembly of 1,3-dimethylimidazol-2-ylidene (IMe), a prototypical NHC, on Cu(111), Ag(111), and Au(111) surfaces using STM (scanning tunneling microscopy) and XPS (X-ray photoelectron spectroscopy), it was observed that IMe dimers fused by a single coinage metal atom were the preferred structures. , …”

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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“…The electronic ground state of this radical has 3 Σ − symmetry. Its vibrational spectrum has been studied both in rare-gas matrices [7,8,9] and in the gas phase using laser induced fluorescence (LIF) techniques [10]. The first excited electronic state, of 3 Π symmetry, has been recently investigated both in the gas phase, using LIF techniques, [10,11] and in rare gas matrices [12].…”

Section: Introductionmentioning

confidence: 99%