: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Modeling metal-catalyzed polyethylene depolymerization: [(Phen)Pd(X)]+(X = H and CH3) catalyze the decomposition of hexane into a mixture of alkenes via a complex reaction network

This paper presents the first general examples of palladium-catalyzed desulfinative cross-coupling reaction of polyhalogenated aryl triflates with aryl sulfinate salts showing an inversion of the conventional reactivity order of C—Br > C—Cl > C—OTf. The catalyst system, comprising of Pd(OAc)2 and tBuPhSelectPhos, exhibited excellent catalytic reactivity and chemoselectivity toward this reaction. This reaction had a wide range of substrate scopes and provided a simple and efficient method for the construction of functionalized biaryl motifs. Notably, the C—H···Pd interaction from the methine hydrogen of the C2-cyclohexyl group of the indolyl phosphine ligand with the Pd center may contribute a key factor in reactivity and chemoselectivity. Assisting with density functional theory (DFT) calculations, the results revealed that the oxidative addition step in this reaction was a controlling-chemoselectivity step. Appendix S1: Supplement Information Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. 

Palladium‐Catalyzed
 Desulfinative
 Cross‐Coupling
 of Polyhalogenated Aryl Triflates with Aryl Sulfinate Salts: Inversion of Traditional Chemoselectivity

A Two-Step Catalytic Cycle for the Acceptorless Dehydrogenation of Ethane by Group 10 Metal Complexes: Role of the Metal in Reactivity and Selectivity

The gas-phase extrusion–insertion (ExIn) reactions of the palladium complexes [(phen)nPd(O2SC6H5)]+ (phen = 1,10-phenanthroline, n = 1 or 2), were investigated in the gas phase by multistage mass spectrometry (MSn) experiments consisting of electrospray ionisation and a linear ion trap combined with density functional theory (DFT) calculations. Desulfination of palladium sulfinate cations under collision-induced dissociation (CID) generates the organopalladium intermediates [(phen)nPd(C6H5)]+. Of these two organometallic cations, only [(phen)Pd(C6H5)]+ reacts with phenyl isocyanate via insertion to yield [(phen)Pd(NPhC(O)C6H5)]+. The formation of a coordinated amidate anion is supported by DFT calculations. In exploring this reactivity in the solution phase, we found that heating a mixture of benzenesulfinic acid, phenylisocyanate and palladium trifluoroacetate under a range of different conditions (ligand free versus with ligand, different solvents, addition of acid or base) failed to lead to the formation N-phenyl-benzamide in all cases. Instead, biphenyl was formed and could be isolated in a yield of 46%. DFT calculations using a solvent continuum reveal that the barrier associated with the insertion reaction lies above the competing sequential reactions of desulfination of a second phenyl sulfinate followed by reductive elimination of biphenyl. 

/pdf/why-does-the-synthesis-of-n-phenylbenzamide-from-94ri3drz.pdf

Why does the synthesis of N-phenylbenzamide from benzenesulfinate and phenylisocyanate via the palladium-mediated Extrusion–Insertion pathway not work? A mechanistic exploration

Desulfination versus decarboxylation as a means of generating three- and five-coordinate organopalladium complexes [(phen)nPd(C6H5)]+ (n = 1 and 2) to study their fundamental bimolecular reactivity

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Desulfination versus decarboxylation as a means of generating three- and five-coordinate organopalladium complexes [(phen)nPd(C6H5)]+ (n = 1 and 2) to study their fundamental bimolecular reactivity