This paper reports preparation, characterization, and reactivity of iodosylarene adducts of a manganese(IV) salen complex. In order to systematically investigate steric and electronic factors that control reactivity and selectivity, we prepared iodosylarene adducts from iodosylbenzene, iodosylmesitylene, 2,4,6-triethyliodosylbenzene, and pentafluoroiodosylbenzene. We also investigated the effect of anions on I(III) by using chloride, benzoate, and p-toluenesulfonate. Spectroscopic studies using (1)H NMR, electron paramagnetic resonance, infrared spectroscopy, and electrospray ionization mass spectrometry show that these iodosylarene adducts are manganese(IV) complexes bearing two iodosylarenes as external axial ligands. Reactions with thioanisole under the pseudo-first-order conditions show that the electron-withdrawing pentafluorophenyl group and the p-toluenesulfonate anion on I(III) significantly accelerate the oxygen-atom transfer. The high reactivity is correlated with a weakened I-OMn bond, as indicated by IR spectroscopy and mass spectrometry. Stoichiometric reactions with styrenes show that both enantioselectivity and diastereoselectivity are dependent on the arenes and anions on I(III) of the coordinate iodosylarenes. Notably, the pentafluorophenyl group and the p-toluenesulfonate anion suppress the cis-to-trans isomerization in the epoxidation of cis-β-methylstyrene. The present results show that iodosylarene adducts of manganese(IV) salen complexes are indeed active oxygen-atom-transfer reagents and that their reactivity and selectivity are regulated by steric and electronic properties of the arenes and anions on I(III) of the coordinated iodosylarenes.
Identification of methyl acetate in the interstellar medium (ISM) and its spectroscopic studies have prompted us to investigate the structure of crystalline methyl acetate using numerical calculations. Here, we present a theoretical study of the structure of crystalline methyl acetate and its isotopologues and compare the calculated infrared (IR) spectra with the available experimental data. The optimized structure and vibrational properties were calculated using SIESTA software at 0 K. In the optimization process, the Perdew-Burke-Ernzerhof functional and conjugate gradient methods were used with double zeta polarization basis functions. After optimization of the periodic structure, the vibrational frequencies and normal modes were calculated within the harmonic approximation. Using the calculated results, we refine the mode assignments of experimental work on crystalline methyl acetate and determine the low frequency modes (below 650 cm(-1)). To investigate the accuracy of the pseudopotential and confirm the IR frequencies, we performed molecular calculations using a periodic model of methyl acetate and its isotopologues using SIESTA and compared them with results obtained from Gaussian 09 (all electron method) calculations. Finally, we assigned the vibrational modes of crystalline CD3-COO-CH3 and CH3-COO-CD3, for which experimental data are not available in the crystalline phase under ISM conditions. For all of the calculation methods, the IR vibrational modes of molecular and crystalline methyl acetate and its isotopologues were in good agreement with the available experimental data and predict the unavailable values.
The title hydroxylamine (NT) undergoes pyrene-sensitized photodecomposition to give rearrangement and fragmentation products. An analysis of linear Stern–Volmer plots, both for the sensitized photolysis of NT and for the fluorescence quenching of pyrene by NT, indicates the involvement of singlet pyrene in this photolysis. The observation of negligible effects of 1,3-cyclohexadiene and trans-stilbene as a triplet quencher on the reaction provides further supporting evidence for a singlet-pathway mechanism. A comparison of the relative state energies of NT and the sensitizer suggests the existence of a reactive singlet-exciplex intermediate formed between the singlet-state sensitizer and the ground-state NT. The results of solvent and micellar effects on the sensitized photolysis establish that electron transfer in the exciplex predominates in a polar solvent, and that in a nonpolar solvent energy transfer in this exciplex plays a major role in the reaction.
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