Post–Hartree–Fock MP2 and density functional theory derived structure and vibrations of 1,2-dithiole-2-thione and 1,2-dithiole-3-one

Fabian, Jürgen; Herzog, K.

doi:10.1016/s0924-2031(97)00043-x

Cited by 13 publications

(3 citation statements)

References 35 publications

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“…Extensive electronic structure and spectroscopic studies of metallo-bis(dithiolenes) have been undertaken as a result of their potential involvement in electrically conducting (115,116,142,145,146,201,202,270,359,(361)(362)(363) and optoelectronic device technologies (113,119,160,248,(364)(365)(366)(367)(368)(369)(370)(371)(372)(373)(374), as well as their presence in the active sites of certain pyranopterin Mo and pyranopterin W enzymes (11, 13, 17, 19, 27, 28, 36, 45- There have been a considerable number of MO calculations performed on four-coordinate square-planar metallo-bis(dithiolene) complexes at various levels of theory (283,327,328,(379)(380)(381)(382)(383)(384). The most important differences in the results of these various calculations rests in the energy level ordering of the valence MOs as well as the degree of metal-sulfur covalency.…”

Section: Metallo-bis(dithiolenes)mentioning

confidence: 99%

The Electronic Structure and Spectroscopy of Metallo‐Dithiolene Complexes

Kirk

McNaughton

Helton

2003

Progress in Inorganic Chemistry

119

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Section: Metallo-bis(dithiolenes)mentioning

confidence: 99%

The Electronic Structure and Spectroscopy of Metallo‐Dithiolene Complexes

Kirk

McNaughton

Helton

2003

Progress in Inorganic Chemistry

119

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“…DFT is typically more accurate than HF, especially in the case when heavy atoms are contained in the molecular structure. The improved accuracy of DFT, however, comes at the cost of increased computational time (19,20). Results obtained with both of these methods also depend significantly on the size of the basis set used to represent molecular electronic wave functions (orbitals).…”

Section: Experimental and Computational Proceduresmentioning

confidence: 99%

Educational Applications of Infrared and Raman Spectroscopy: A Comparison of Experiment and Theory

et al. 2000

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Advances in Raman spectroscopy and computer technology facilitate the introduction of current spectroscopic and molecular modeling methods at the undergraduate level. This study compares experimental infrared (IR) and Raman spectra of selected molecules to calculated spectra using semiempirical and ab initio methods. These illustrate the complimentary nature of IR and Raman spectroscopies as well as the limitation and successes of computational methods in predicting molecular vibrational frequencies and intensities. Particular examples used to illustrate these principles include comparisons of cis- and trans-1,2-dichloroethene as well as methanol and d1 -methanol. The former comparison illustrates symmetry selection rules, and the latter demonstrates the use of isotopic substitution in the assignment of vibrational spectra.

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“…The sulfur ring does not display a sizable aromatic character, in agreement with the previously reported structures and theoretical computations. But the most exciting finding was the formation of another product ( 5 ) that does not contain phosphorus. It, apparently, results from the unprecedented conversion of a phosphole sulfide into a thiophene ring.…”

mentioning

confidence: 99%

An Unexpected Sequence: From Phosphole Sulfide to Phosphole- and Thiophene-Annulated 1,2-Dithiole-3-thiones

Ćirić

Mathey

2009

Organometallics

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The deprotonation of 1-phenyl-3,4-dimethylphosphole sulfide by a bulky base, followed by the reaction of S 2 Cl 2 , unexpectedly yields a phosphole-annulated 1,2-dithiole-3-thione. The complexation of this product by [W(CO) 5 ] takes place at CdS as expected on the basis of theoretical calculations. Another product results from the unprecedented replacement of the P(S)Ph unit by sulfur, giving the corresponding thiophene derivative.The easily accessible 3H-1,2-dithiole-3-thiones 1 display an interesting redox chemistry, can serve as ligands for transition metals, and have a lot of interesting biological properties. It would be quite interesting to combine this structure with a modulating phosphino group, but, to the best of our knowledge, no phosphino-substituted dithiolethione has ever been described in the literature until now. We describe herein how we found an original phosphole-annulated dithiolethione while trying to link two phosphole units by a sulfur bridge.Our starting point was the delocalized anion obtained by deprotonation of 1-phenyl-3,4-dimethylphosphole sulfide (1) by a bulky base (here the sodium hexamethyldisilazide). 2 We investigated the reaction of this anion with disulfur dichloride with the aim of creating a S-S link between two phosphole units. In fact, we obtained a complicated mixture of products, among which a readily eluted deep red compound (2) was especially noteworthy (eq 1).The formula of 2 was established as follows. The measured mass, m/z 312.9398 (MH þ ), was very close to the computed mass for C 12 H 10 PS 4 (312.9403). The proton NMR spectrum showed only one olefinic R-proton at δ 6.19 ppm ( 2 J H-P = 32.24 Hz) and one methyl at δ 2.61 ppm (CD 2 Cl 2 ). The most prominent feature of the 13 C NMR spectrum was a CdS doublet at δ 209.61 ppm (J C-P = 16.5 Hz). Classical dithiolethiones show a CdS resonance in the range 206-216 ppm. 1 The characterization of 2 was completed by the X-ray crystal structure analysis of the complex (see later). In order to have a more precise understanding of the electronic structure of 2, we performed a DFT calculation on the model compound 3 at the B3LYP/6-311þG(d,p) level. 3 The computed structure is very close to the experimental structure of the complex. The HOMO (Figure 1) is essentially localized on the dithiolethione ring with no participation of phosphorus. The coefficient at the CdS sulfur is huge, indicating that it will be the reactive site toward electrophiles, as is the case for normal dithiolethiones. The participation of the phosphole ring is more significant in the LUMO. At -5.1, the NICS(1) index 4 indicates that the sulfur ring is only weakly aromatic.The UV/vis spectrum of 2 ( Figure 2) shows a characteristic band at 483 nm (ε 8339). In the parent dithiolethione, this band occurs at 410 nm (ε 6400) and corresponds to a π*rπ Figure 1. HOMO and LUMO of compound 3 as computed at the B3LYP/6-311þG(d,p) level. (3) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vr...

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Post–Hartree–Fock MP2 and density functional theory derived structure and vibrations of 1,2-dithiole-2-thione and 1,2-dithiole-3-one

Cited by 13 publications

References 35 publications

The Electronic Structure and Spectroscopy of Metallo‐Dithiolene Complexes

The Electronic Structure and Spectroscopy of Metallo‐Dithiolene Complexes

Educational Applications of Infrared and Raman Spectroscopy: A Comparison of Experiment and Theory

An Unexpected Sequence: From Phosphole Sulfide to Phosphole- and Thiophene-Annulated 1,2-Dithiole-3-thiones

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