A5102724647- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Chemical Reactions and Mechanisms
- Organometallic Complex Synthesis and Catalysis
- Synthesis and characterization of novel inorganic/organometallic compounds
- Advanced Chemical Physics Studies
- Crystallography and molecular interactions
- Fluorine in Organic Chemistry
- Radical Photochemical Reactions
- Organoboron and organosilicon chemistry
- Synthesis and Catalytic Reactions
- Ferrocene Chemistry and Applications
- Coordination Chemistry and Organometallics
- Photochemistry and Electron Transfer Studies
- Molecular Spectroscopy and Structure
- Atmospheric Ozone and Climate
- Atmospheric chemistry and aerosols
- Organic Chemistry Cycloaddition Reactions
- Free Radicals and Antioxidants
- Metal-Organic Frameworks: Synthesis and Applications
- Spectroscopy and Laser Applications
- Molecular Junctions and Nanostructures
- Metal complexes synthesis and properties
- Chemical Synthesis and Reactions
- Inorganic Fluorides and Related Compounds
Technische Universität Berlin
2021-2024
Tianjin University
2005-2022
Hangzhou Normal University
2018-2021
Hangzhou Academy of Agricultural Sciences
2021
State Council of the People's Republic of China
2021
Soochow University
2017-2019
Nankai University
2018
Suzhou Research Institute
2017-2018
Soochow University
2017
Qujing Normal University
2013
The elusive plumbylone {[Si
The formation of isolable monatomic BiI complexes and BiII radical species is challenging due to the pronounced reducing nature metallic bismuth. Here, we report a convenient strategy tame atoms by taking advantage redox noninnocent character new chelating bis(germylene) ligand. remarkably stable novel cation complex 4, supported bis(iminophosphonamido-germylene)xanthene ligand [(P)GeII(Xant)GeII(P)] 1, [(P)GeII(Xant)GeII(P) = Ph2P(NtBu)2GeII(Xant)GeII(NtBu)2PPh2, Xant...
The monoatomic zero-valent tin complex (stannylone) {[Si
Abstract Chemical reactions involving quantum mechanical tunneling (QMT) increasingly attract the attention of scientists. In contrast to hydrogen‐tunneling as frequently observed in chemistry and biology, solely by heavy atoms is rare. Herein, we report heavy‐atom trifluoroacetyl nitrene, CF 3 C(O)N. The carbonyl nitrene C(O)N triplet ground state was generated cryogenic matrices laser (193 or 266 nm) photolysis characterized IR EPR spectroscopy. theoretically predicted activation barriers...
Abstract The parent thioketene S ‐oxide H 2 CCSO has been generated in the gas phase through flash vacuum pyrolysis (ca. 1000 K) of vinyl sulfoxide CC(Br)−S(O)CF 3 via intermediacy a novel sulfinyl radical C=C(Br)−SO ( syn and anti conformers). Upon irradiation at 266 nm, decomposes into HCCH/SO CS/CO cryogenic Ar matrix. Whereas, visible‐light irradiations result ↔ conformational interconversion C=C(Br)−SO. molecular structures isomers are computationally studied CCSD(T)‐F12/VTZ‐F12 level...
The unprecedented silylene-supported dibenzodiboraoxepin
Two simple acylnitrenes, 2-furoylnitrene (2) and 3-furoylnitrene (6), were generated through 266 nm laser photolysis of the corresponding azides. Both are magnetically bistable in cryogenic matrices, as evidenced by direct observation closed-shell singlet state with IR spectroscopy solid Ne, Ar, Kr, Xe, N2 matrices (3-40 K) triplet toluene (10 EPR (32: |D/hc| = 1.48 cm-1 |E/hc| 0.029 cm-1; 36: 1.39 |E/hc|c 0.039 cm-1). Subsequent visible-light UV irradiations led to formation furyl...
Disulfur dioxide, OSSO, has been proposed as the enigmatic "near-UV absorber" in yellowish atmosphere of Venus. However, fundamentally important spectroscopic properties and photochemistry OSSO are scarcely documented. By either condensing gaseous SO or 266 laser photolysis an S2O2 complex Ar N2 at 15 K, syn-OSSO, anti-OSSO, cyclic OS([double bond, length m-dash]O)S were identified by IR UV/Vis spectroscopy for first time. The observed absorptions (λmax) 517 390 nm coincide with near-UV...
Methoxycarbonylnitrene CH<sub>3</sub>OC(O)N, the missing link in frequently studied Curtius-rearrangement of CH<sub>3</sub>OC(O)N has been directly observed by using matrix-isolation IR and EPR spectroscopy.
When mixing SO with O2 in N2, Ne, or Ar, an end-on complex OS-OO forms the gas phase and can subsequently be trapped at cryogenic temperatures (2.8-15.0 K). Upon infrared light irradiation, converts to SO3 SO2 + O concomitant formation of a rare 1,2,3-dioxathiirane 2-oxide, i.e., cyclic OS([double bond, length as m-dash]O)O. Unexpectedly, ring-closure 16OS-18O18O yields ca. 2 : 1 mixture 18OS([double m-dash]16O)18O 16OS([double m-dash]18O)18O. The characterization m-dash]O)O IR UV/Vis...
Arylsulfinyl radicals are key intermediates in sulfoxide chemistry. The parent molecule, phenylsulfinyl radical PhSO•, has been generated for the first time gas phase through high-vacuum flash pyrolysis of PhS(O)R (R = CF3 and Cl) at about 1000 K. Upon UV light irradiation (365 nm), PhSO• isomerizes to novel oxathiyl PhOS• cryogenic matrices (2.8 K). Prolonged causes further isomerization 2-hydroxyphenylthiyl radical, formation which also observed 193 nm laser photolysis matrix-isolated...
Abstract Chemical reactions involving quantum mechanical tunneling (QMT) increasingly attract the attention of scientists. In contrast to hydrogen‐tunneling as frequently observed in chemistry and biology, solely by heavy atoms is rare. Herein, we report heavy‐atom trifluoroacetyl nitrene, CF 3 C(O)N. The carbonyl nitrene C(O)N triplet ground state was generated cryogenic matrices laser (193 or 266 nm) photolysis characterized IR EPR spectroscopy. theoretically predicted activation barriers...
Abstract Neutral five‐atomic cumulenes formally consisting of two pseudohalogens (e.g., NCO, NNN, NSO) by sharing the central nitrogen atom are exotic species that have been barely studied. Through flash vacuum pyrolysis CF 3 S(O)NCO at ca. 1200 K, sulfinyl isocyanate, bearing resonance structures O=C−N=S=O and O=C=N−S=O, has generated in gas phase subsequently characterized cryogenic matrices (Ar N 2 ). Its reversible conformational (syn anti) interconversion photodecomposition were observed.
S-Nitrosothiols (RSNO) are exogenous and endogenous sources of nitric oxide in biological systems due to facile homolytic cleavage the S-N bonds. By following photolytic decomposition prototypical RSNO (R = Me Et) Ne, Ar, N2 matrixes (<10 K), elusive caged radical pairs consisting (NO•) thiyl radicals (RS•), bridged by O···S H···N connections, were identified with IR UV/vis spectroscopy. Upon red-light irradiation, both (RS•···•ON) vanish reform RSNO. According calculation at...
Abstract Two hitherto unreported sulfur‐centered radicals CF 3 SO . and OS were generated in the gas phase through high‐vacuum flash pyrolyses of sulfoxide S(O)X (X=CF , Cl, PhO) precursors. The molecule is first experimental example that constitutes an oxathiyl radical. It was isolated characterized by combining matrix‐isolation IR UV/Vis spectroscopy with quantum chemical computations up to UCCSD(T)‐F12/cc‐pVTZ‐F12 level theory. Upon UV light irradiation (254 or 266 nm), sulfinyl radical...
The decomposition of phenyl azidoformate, PhOC(O)N3, was studied by combining matrix isolation spectroscopy and quantum chemical calculations. Upon UV laser photolysis (193 266 nm), the azide isolated in cryogenic noble gas matrices (Ne Ar, 2.8 K) decomposes into N2 a novel oxycarbonylnitrene PhOC(O)N, which identified matrix-isolation IR (with 15N labeling) EPR (|D/hc| = 1.620 cm-1 |E/hc| 0.024 cm-1). Subsequent visible-light irradiation (532 nm) causes rearrangement nitrene phenoxy...
Methylsulfoxide radicals CH3SOx (x = 1-4) are key reactive sulfur species (RSS) in the atmospheric oxidation of volatile organic compounds (VOSCs). Through flash vacuum pyrolysis (FVP) trifluoromethanesulfinic acid methyl ester CF3S(O)OCH3 at 1000 K, methoxysulfinyl radical CH3OSO has been generated gas phase and subsequently characterized cryogenic N2, Ar, Ne matrices by IR spectroscopy. Upon 266 nm laser irradiation, efficiently isomerizes to less stable methylsulfonyl CH3SO2 without...
<italic>N</italic>-Methylcarbamoyl azide has been characterized and the nitrene intermediate in its Curtius-rearrangement observed two conformations by matrix-isolation IR EPR spectroscopy.
An exotic ternary S, N, O heterocumulene OSNSO in syn-syn (A) and syn-anti (B) conformations has been generated the gas phase through flash vacuum pyrolysis of CF3S(O)NSO at 700 K. Upon visible light irradiation (570 ± 20 or 532 nm), both A B, isolated cryogenic matrices (N2, Ne, Ar, Kr, <30 K), convert to a higher-energy anti-anti conformer (C). The reverse conformational transformation occurs either S═N bond rotation (C B) under (400 nm) 2.8 K thermal nitrogen inversion A) temperature...
Unlike a triplet spin-state for alkyl- and aryl-sulfonylnitrenes, theoretical computations suggest closed-shell singlet (CSS) ground state simple sulfamoylnitrenes R2NS(O)2-N (R = H Me) due to intramolecular NN interactions. Experimentally, both sulfamoylnitrenes, generated in the laser photolysis of corresponding azides, were isolated as evidenced by EPR (5 K) IR (3 spectroscopy. The formation higher-energy is reasonably explained change spin from initially CSS through low-energy minimum...
A cyclic (R2 SnAu)3 anion (3- , R2 Sn=2,2,5,5-tetrakis(trimethylsilyl)-1-stannacyclopentane-1,1-diyl) has been synthesized as a stable blue salt with K+ (THF)6 through the reaction of dialkylstannylene 1 R'3 PAuCl (R'=Et, Ph) followed by reduction KC8 . Crystallographic and NMR analysis shows that six-membered (SnAu)3 ring 3- is planar highly symmetric an equal distance six Au-Sn bonds. UV/Vis spectrum in hexane reveals intense absorption maximum at 598 nm. While Au3- four valence electrons...
Abstract The monoatomic zero‐valent tin complex (stannylone) {[Si II (Xant)Si ]Sn 0 } 5 stabilized by a bis(silylene)xanthene ligand, [Si =PhC(NtBu) 2 Si(Xant)Si(NtBu) CPh], and its bis‐tetracarbonyliron [Fe(CO) 4 ] are reported. stannylone bearing two‐coordinate atom is synthesized reduction of the precursor with potassium graphite. Compound results from Sn halide Cl}Cl or ]SnBr 3 through reductive salt‐metathesis reaction K Fe(CO) . According to density functional theory (DFT)...
Sulfonyl azide isocyanate, (OCN)S(O)2N3, was prepared and characterized by IR (gas, matrix-isolation), Raman (liquid), UV-vis spectroscopy. Upon flash vacuum pyrolysis (FVP) at ca. 1000 K, gaseous (OCN)S(O)2N3 decomposes completely yields fragments N2, SO2, SO3, NCN, N3, NCO, CO, CN, NO. In contrast, the splits off N2 furnishes a transient triplet sulfonyl nitrene intermediate (OCN)S(O)2N upon 266 nm laser irradiation in solid Ne-matrix 2.8 K. Subsequent photolysis of with visible light (λ =...