Parent Thioketene S‐Oxide H₂CCSO: Gas‐Phase Generation, Structure, and Bonding Analysis

Abstract

The parent thioketene S-oxide H CCSO has been generated in the gas phase through flash vacuum pyrolysis (ca. 1000 K) of vinyl sulfoxide H CC(Br)-S(O)CF via the intermediacy of a novel vinyl sulfinyl radical H C=C(Br)-SO (syn and anti conformers). Upon irradiation at 266 nm, H CCSO decomposes into HCCH/SO and H CS/CO in cryogenic Ar matrix. Whereas, visible-light irradiations result in syn↔anti conformational interconversion in H C=C(Br)-SO. The molecular structures of H CCSO and isomers are computationally studied at the CCSD(T)-F12/VTZ-F12 level of theory, and the bonding properties of H CCSO are analyzed with the EDA-NOCV method at the M06-2X/TZ2P level.

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)3(M=Sr, Ba)

“…It has been shown by us in numerous studies that those fragments, which give the smallest absolute values for the orbital term Δ E orb , are the most suitable species to represent the bonding of the complex, since they change the least in the formation of the bond. This method has proven to be very helpful for a large number of chemical compounds whose nature is not directly apparent . Tables S4–S6 show that the Δ E orb values using atom M in the electronic ground state and (Bz) 3 in the excited state are significantly larger than those in Table .…”

“…Therefore, we used the BP86‐D3(BJ) functional in conjunction with the TZ2P basis set. Our experience in numerous studies has shown that the EDA‐NOCV calculations are not very sensitive to the functional . Table gives the numerical results of the calculations of M(Bz) 3 (M=Ca, Sr, Ba) at the D 3 equilibrium structures.…”

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)3(M=Sr, Ba)

“…nature is not directly apparent. [27][28][29][30][31][32][33][34][35][36][37] Tables S4-S6 show that the DE orb values using atom Minthe electronic ground state and (Bz) 3 in the excited state are significantly larger than those in Table 4. However,t here is an alternative option for the choice of the interacting fragments.T he calculated partial charges of M(Bz) 3 using the NBO 6.0 method [38] suggest large positive charges for the metal atoms of 1.47 for Ca, 1.46 for Sr and 1.40 for Ba.…”

“…Our experience in numerous studies has shown that the EDA-NOCV calculations are not very sensitive to the functional. [27][28][29][30][31][32][33][34][35][36][37] Table 4gives the numerical results of the calculations of M(Bz) 3 (M = Ca, Sr, Ba) at the D 3 equilibrium structures.…”

Intermediates of Carbon Monoxide Oxidation on Praseodymium Monoxide Molecules: Insights from Matrix-Isolation IR Spectroscopy and Quantum-Chemical Calculations

“…Note that the answer will shape the bonding situations of the two interacting fragments. To address the above question, an EDA-NOCV analysis with alternative reference fragments is carried out because of its ability to determine the most appropriate bonding fragments by giving the minimum orbital interactions Δ E orb . − In addition, the EDA-NOCV method has been proven to provide detailed insight into the interaction nature of the bonding fragments. Table presents a numerical comparison of the EDA-NOCV calculation results for the two intermediates using neutral or ionic fragments.…”