Experimentally Delineating the Catalytic Effect of a Single Water Molecule in the Photochemical Rearrangement of the Phenylperoxy Radical to the Oxepin-2(5)-one-5-yl Radical.

Catalysis plays a pivotal role in both chemistry and biology, primarily attributed to its ability to stabilize transition states and lower activation free energies, thereby accelerating reaction rates. While computational studies have contributed valuable mechanistic insights, there remains a scarcity of experimental investigations into transition states. In this work, we embark on an experimental exploration of the catalytic energy lowering associated with transition states in the photorearrangement of the phenylperoxy radical-water complex to the oxepin-2(5)-one-5-yl radical.

The enol of isobutyric acid.

We present the gas-phase synthesis of 2-methyl-prop-1-ene-1,1-diol, an unreported higher energy tautomer of isobutyric acid. The enol was captured in an argon matrix at 3.5 K, characterized spectroscopically and by DFT computations.

Preparation and Photochemistry of Parent Triplet Vinylarsinidene.

Vinyl pnictinidenes are an elusive family of molecules that have been suggested as key intermediates in multiple chemical reactions and commonly display a predisposition toward open-shell electronic ground states (as is evident from quantum chemical computations). However, owing to their expected extremely high reactivity, no vinyl pnictinidene has ever been isolated and characterized spectroscopically. Here, we report the synthesis and spectroscopic characterization of vinylarsinidene, a higher congener of vinylnitrene.

On-Surface Synthesis and Real-Space Visualization of Aromatic P N.

On-surface synthesis is at the verge of emerging as the method of choice for the generation and visualization of unstable or unconventional molecules, which could not be obtained via traditional synthetic methods. A case in point is the on-surface synthesis of the structurally elusive cyclotriphosphazene (P N ), an inorganic aromatic analogue of benzene. Here, we report the preparation of this fleetingly existing species on Cu(111) and Au(111) surfaces at 5.

The enol of propionic acid.

We demonstrate the gas-phase synthesis of prop-1-ene-1,1-diol, the hitherto unreported higher energy tautomer of propionic acid. The enol was trapped in an argon matrix and characterized by IR and UV/Vis spectroscopy in combination with density functional theory computations. Upon photolysis, the enol rearranges to propionic acid and methylketene.

Triplet Phenylarsinidene and Its Oxidation to Dioxophenylarsine.

Carbenes and nitrenes are key intermediates involved in numerous chemical processes, and they have attracted considerable attention in synthetic chemistry, biochemistry, and materials science. Even though parent arsinidene (H-As) has been characterized well, the high reactivity of subsituted arsinidenes has prohibited their isolation and characterization to date. Here, we report the preparation of triplet phenylarsinidene through the photolysis of phenylarsenic diazide isolated in an argon matrix and its subsequent characterization by infrared and UV/vis spectroscopy.

Selective Preparation of Phosphorus Mononitride (P≡N) from Phosphinoazide and Reversible Oxidation to Phosphinonitrene.

The interstellar candidate phosphorus mononitride PN, a metastable species, was generated through high-vacuum flash pyrolysis of (o-phenyldioxyl)phosphinoazide in cryogenic matrices. Although the PN stretching band was not directly detected because of its low infrared intensity and possible overlaps with other strong bands, o-benzoquinone, carbon monoxide, and cyclopentadienone as additional fragmentation products were clearly identified. Moreover, an elusive o-benzoquinone-PN complex formed when (o-phenyldioxyl)phosphinoazide was exposed to UV irradiation at λ=254 nm.

Matrix isolation and photorearrangement of - and -1,2-ethenediol to glycolaldehyde.

1,2-Ethenediols are deemed key intermediates in prebiotic and interstellar syntheses of carbohydrates. Here we present the gas-phase synthesis of these enediols, the high-energy tautomers of glycolaldehyde, trapped in cryogenic argon matrices. Importantly, upon photolysis at = 180-254 nm, the enols rearrange to the simplest sugar glycolaldehyde.

Generation and reactivity of vinyltelluryl radical.

Vinyltelluryl radical was prepared by high-vacuum flash pyrolysis from the corresponding divinylditelluride and trapped in an argon matrix at 10 K. The title compound was characterized by IR and UV/Vis spectroscopy, and all experimental data match well with density functional theory at the UB3LYP/def2-QZVPP level. According to UB3LYP/def2-QZVPP computations, the spin density is mainly localized on the Te atom.

Preparation and characterization of the enol of acetamide: 1-aminoethenol, a high-energy prebiotic molecule.

Amide tautomers, which constitute the higher-energy amide bond linkage, not only are key for a variety of biological but also prebiotic processes. In this work, we present the gas-phase synthesis of 1-aminoethenol, the higher-energy tautomer of acetamide, that has not been spectroscopically identified to date. The title compound was prepared by flash vacuum pyrolysis of malonamic acid and was characterized employing matrix isolation infrared as well as ultraviolet/visible spectroscopy.

1,1,2-Ethenetriol: The Enol of Glycolic Acid, a High-Energy Prebiotic Molecule.

As low-temperature conditions (e.g. in space) prohibit reactions requiring large activation energies, an alternative mechanism for follow-up transformations of highly stable molecules involves the reactions of higher energy isomers that were generated in a different environment.

Isolation and Characterization of the Free Phenylphosphinidene Chalcogenides C H P=O and C H P=S, the Phosphorous Analogues of Nitrosobenzene and Thionitrosobenzene.

The structures and reactivities of organic phosphinidene chalcogenides have been mainly inferred from trapping or complexation experiments. Phosphinidene chalcogenide derivatives appear to be an elusive family of molecules that have been suggested as reactive intermediates in multiple organophosphorus reactions. The quest to isolate "free" phosphinidene chalcogenides remains a challenge in the field.

1,1-Ethenediol: The Long Elusive Enol of Acetic Acid.

We present the first spectroscopic identification of hitherto unknown 1,1-ethenediol, the enol tautomer of acetic acid. The title compound was generated in the gas phase through flash vacuum pyrolysis of malonic acid at 400 °C. The pyrolysis products were subsequently trapped in argon matrices at 10 K and characterized spectroscopically by means of IR and UV/Vis spectroscopy together with matching its spectral data with computations at the CCSD(T)/cc-pCVTZ and B3LYP/6-311++G(2d,2p) levels of theory.

Spectroscopic identification of the phenyltelluryl radical and its reactivity toward molecular oxygen.

The phenyltelluryl radical was prepared by high-vacuum flash pyrolysis of diphenyl ditelluride and was chacracterized by matrix isolation IR and UV/Vis spectroscopy. After doping the matrix with molecular oxygen and allowing bimolecular reactions, the hitherto unkown phenyltelluro peroxy radical formed and was identified via IR spectroscopy. Irradiation with light at λ = 436 nm leads to isomerization to the thermodynamically more stable novel phenyltelluroyl radical.

Preparation and spectroscopic identification of methyl-Se-nitrososelenol.

Herein, we report, for the first time, the preparation, matrix-isolation, and spectroscopic characterization of the methyl selenyl radical and methyl-Se-nitrososelenol in combination with DFT and CASSCF/NEVPT2 computations. The latter proved to be highly photolabile, and upon irradiation with light at λ = 465 nm it leads to methyl selenyl and nitric oxide radical pairs. Upon λ > 730 nm irradiation it rearranges back to methyl-Se-nitrososelenol.

Generation and Spectroscopic Identification of the Thiuram Radical (CH)NCS.

We report the first preparation, matrix-isolation, and IR and UV/vis spectroscopic characterization of the thiuram radical that is a highly important species for many industrial processes. The thiuram radical was prepared by thermal dissociation of tetramethylthiuram disulfide and was identified by matching its spectroscopic data with density functional theory [UB3LYP/6-311++G(3df,3pd)] computations. The title compound proved to be highly photolabile, and irradiation with light at λ = 623 nm affords a hitherto unknown carbamodithioic acid, N-(methyl)- N-methyl radical, as characterized by IR and UV/vis spectroscopy in low-temperature matrices.

Caged Nitric Oxide-Thiyl Radical Pairs.

S-Nitrosothiols (RSNO) are exogenous and endogenous sources of nitric oxide in biological systems due to facile homolytic cleavage of the S-N bonds. By following the photolytic decomposition of prototypical RSNO (R = Me and Et) in Ne, Ar, and N matrixes (<10 K), elusive caged radical pairs consisting of nitric oxide (NO•) and thiyl radicals (RS•), bridged by O···S and H···N connections, were identified with IR and UV/vis spectroscopy. Upon red-light irradiation, both caged radical pairs (RS•···•ON) vanish and reform RSNO.

Photochemical reactions of triplet phenylphosphinidene with carbon monoxide and nitric oxide.

Here we report the photochemical reactions of triplet phenylphosphinidene with carbon monoxide and nitric oxide. The photolysis of phenylphosphirane in carbon monoxide-doped matrices enabled the first spectroscopic identification of phenylphosphaketene, the hitherto unreported phosphorus analogue of phenyl isocyanate. The hitherto undisclosed phosphinimine-N-oxyl radical formed upon UV irradiation of the phenylphosphinidene with nitric oxide in argon matrices at 10 K.

Unravelling Lawesson's reagent: the structure of monomeric (4-methoxyphenyl)phosphine disulfide.

We describe the isolation as well as IR and UV/Vis spectroscopic characterization of (4-methoxyphenyl)phosphine disulfide in argon matrices at 10 K. The title compound proved to be highly photolabile; irradiation with UV light (λ = 334 nm) led to rearrangement to the equally unreported 3-(4-methoxyphenyl)-1,2,3-dithiaphosphirane. Photoreversion can be achieved upon irradiation at λ = 465 nm.

Atmospherically Relevant Radicals Derived from the Oxidation of Dimethyl Sulfide.

The large number and amounts of volatile organosulfur compounds emitted to the atmosphere and the enormous variety of their reactions in various oxidation states make experimental measurements of even a small fraction of them a daunting task. Dimethyl sulfide (DMS) is a product of biological processes involving marine phytoplankton, and it is estimated to account for approximately 60% of the total natural sulfur gases released to the atmosphere. Ocean-emitted DMS has been suggested to play a role in atmospheric aerosol formation and thereby cloud formation.

The phenylselenyl radical and its reaction with molecular oxygen.

The current study focuses on the generation, identification, and characterization of the phenylselenyl radical using the matrix isolation technique in combination with density functional theory (B3LYP/cc-pVTZ) computations. The hitherto unknown phenylselenyl peroxy radical was synthesized by co-condensation of the phenylselenyl radical with molecular ground state triplet oxygen from the gas phase and subsequent trapping in argon matrices at 10 K. The experimental IR spectra including O isotopically labelled materials compare well with the data obtained from B3LYP/cc-pVTZ computations.

Aliphatic C-H Bond Iodination by a N-Iodoamide and Isolation of an Elusive N-Amidyl Radical.

Contrary to C-H chlorination and bromination, the direct iodination of alkanes represents a great challenge. We reveal a new N-iodoamide that is capable of a direct and efficient C-H bond iodination of various cyclic and acyclic alkanes providing iodoalkanes in good yields. This is the first use of N-iodoamide for C-H bond iodination.

Preparation and Characterization of Parent Phenylphosphinidene and Its Oxidation to Phenyldioxophosphorane: The Elusive Phosphorus Analogue of Nitrobenzene.

Triplet phenylphosphinidene was prepared by light-induced elimination of ethylene from the corresponding phenylphosphirane and was characterized by IR and UV/vis spectroscopy together with matching of its spectral data with density functional theory computations. The photolysis of phenylphosphirane in P-O doped matrices enabled the spectroscopic identification of a hitherto unknown phenyldioxophosphorane, the long elusive phosphorus analogue of nitrobenzene.

Conformer-specific hydrogen atom tunnelling in trifluoromethylhydroxycarbene.

Conformational control of organic reactions is at the heart of the biomolecular sciences. To achieve a particular reactivity, one of many conformers may be selected, for instance, by a (bio)catalyst, as the geometrically most suited and appropriately reactive species. The equilibration of energetically close-lying conformers is typically assumed to be facile and less energetically taxing than the reaction under consideration itself: this is termed the 'Curtin-Hammett principle'.

Generation and characterization of the phenylthiyl radical and its oxidation to the phenylthiylperoxy and phenylsulfonyl radicals.

The phenylthiyl radical (1) was prepared in the gas phase by vacuum flash pyrolysis of allylphenyl sulfide or diphenyl sulfide and isolated in an argon matrix. The hitherto unknown phenylthiyl peroxy radical was synthesized by co-condensation of 1 with molecular oxygen. Irradiation with light of λ = 465 nm led to a rearrangement to the novel phenylsulfonyl radical.