Disulfur Monoxide Research Articles

Electronic structure and coordinate bonding nature of manganese(I) disulfur monoxide complex [MnS2O

Relativistic ab initio molecular orbital calculations have been performed on S2O and [MnS2O]+ in order to investigate the nature and energetics of the interaction between the metal and S2O ligand. The results suggest that the main bonding interactions between the fragment Mn+ and S2O is the σ and π-donative interactions and there is no π back transfer from the disulfur monoxide ligand to manganese. The interactions of π type are weaker. For the coordinated S2O moiety, the unsubstituted sulfur S2 is the electrophilic sile and the exocyclic oxygen and substituted sulfur S1 are nucleophilic sites. The electronic structure of [MnS2O]+ is analyzed in detail as measured by Wiberg's bond indices, charge distributions and orbital populations.

The vibronically-resolved emission spectrum of disulfur monoxide (S2O): An algebraic calculation and quantitative interpretation of Franck–Condon transition intensities

Emission spectra obtained from jet-cooled disulfur monoxide (S2O) molecules have been interpreted by means of a novel Lie algebraic formalism that makes possible the facile evaluation of multidimensional Franck–Condon factors. Fluorescence accompanying selective excitation of isolated vibronic bands in the S2O C̃ 1A′←X̃ 1A′(π*←π) absorption system has been dispersed under moderate spectral resolution, allowing assignment of ground state levels possessing up to 20 quanta of vibration in the ν2 S–S stretching mode [Evib(X̃)⩽13 900 cm−1]. Aside from providing a rigorous and economical description for the inherently anharmonic nature of highly-excited polyatomic species, our algebraic approach enables quantitative information on molecular wavefunctions to be extracted directly from spectroscopic data. The emerging picture of S2O vibrational dynamics suggests that the X̃ 1A′ potential surface is substantially more “local” in character than the C̃ 1A′ manifold. While the observed pattern of X̃ 1A′ vibrational energies could be reproduced well through use of model Hamiltonians that include only diagonal anharmonicities in the local algebraic basis, successful treatment of the C̃ 1A′ state necessitated explicit incorporation of off-diagonal anharmonicities that lead to pervasive mixing of local vibrational character. This disparate behavior is manifest strongly in measured C̃–X̃ transition strengths, thereby allowing detailed investigations of Franck–Condon intensities to discern the underlying dynamics. Structural parameters deduced from algebraic analyses are in good accord with previous predictions of the change in S2O geometry accompanying π*←π excitation.

Reactions of Transition-Metal Cyclopropyl and η1-Allyl Complexes with Sulfur Dioxide and Disulfur Monoxide

The preparations of several cyclopentadienyl iron dicarbonyl cyclopropyl and η1-allyl complexes as well as (Me2PhP)(CO)4 manganese allyl complexes are reported. The iron complexes participated in 3 + 2 cycloaddition reactions with sulfur dioxide (SO2) and disulfur monoxide (S2O) to yield regioisomeric transition-metal substituted 1,2-oxathiolane 1-oxides (sulfenate esters) and 1,2-dithiolane 1-oxides (thiosulfinate esters), respectively. The manganese allyl complexes reacted with both SO2 and S2O to produce insertion products.

Algebraic approach for the calculation of polyatomic Franck–Condon factors.: Application to the vibronically resolved emission spectrum of S 2O

Emission spectra obtained from jet-cooled disulfur monoxide (S 2O) molecules have been interpreted quantitatively by means of a U(2) Lie algebraic theory. Fluorescence accompanying selective excitation of the S 2O C ̃ 1 A′← X ̃ 1 A′ ( π ∗← π) absorption system was dispersed under modest resolution, thereby permitting vibrational assignment of ground-state levels possessing up to 20 quanta of the ν 2 S–S stretching mode. Aside from providing a convenient framework for analysis of recorded energy patterns, the algebraic treatment allows for straightforward calculation of multidimensional Franck–Condon factors and corresponding transition intensities. The emerging picture of S 2O vibrational dynamics suggests that the X ̃ 1 A′ potential surface is substantially more `local' in character than the C ̃ 1 A′ manifold.

Is Disulfur Monoxide a Second Absorber on Venus?

The diminished spherical albedo of Venus from 200 to 500 nm requires at least two different absorbers in the cloud layer. SO2has been identified as the dominant absorber between 200 and 320 nm; however, the identity of the second UV absorber which darkens the planet from 320 to 500 nm remains a mystery. We present the results from photochemical calculations of sulfur oxides in the atmosphere of Venus which indicate that S2O is a strong candidate for the second absorber. The photochemical calculations are constrained by recent observations of SO and SO2by a CU/LASP sounding rocket experiment carried out on 29 March 1991. We calculate that the photochemical lifetime of S2O in the middle atmosphere of Venus is much less than the dynamical mixing time scale, and this can explain the shortest time scales for changes in the dark markings. The calculated vertical profile of S2O from 58 to 96 km is consistent with constraints on the second absorber. In addition, since S2O is chemically derived from SO2, the observed spatial correlation between the second absorber and SO2can be directly explained. The conclusion that S2O is an excellent candidate for the second absorber could be confirmed by laboratory measurements of its absorption cross section.

Cycloaddition reactions of transition-metal 2-alkynyl complexes with a disulfur monoxide source. Transition metal-mediated synthesis of five-membered ring thiosulfinate esters

Cycloaddition reactions of transition-metal 2-alkynyl complexes with a disulfur monoxide source. Transition metal-mediated synthesis of five-membered ring thiosulfinate esters

Unexpected reactions of simple iron alkyls with a thiosulfinate ester capable of serving as a disulfur monoxide source

Attempts to use 4,5-diphenyl-3,6-dihydro-1,2-dithiin-1-oxide as a disulfur monoxide (S 2O) source for S 2O insertion into the metal carbon bond of CpMe n Fe(CO) 2R ( n = 0, 5; R  Me, Et) yielded unexpected iron thioester complexes, CpMe n Fe(CO) 2SC(O)R. The characterization and independent syntheses of these thioester complexes are reported as well as the results of experiments designed to yield some information about the mechanism of formation of these thioester complexes.

Transition-metal-mediated thiosulfinate ester synthesis

Unlike sulfur dioxide (SO{sub 2}), the coordination and organic reaction chemistry of disulfur monoxide (S{sub 2}O) has received little attention. A few Diels-Alder reactions of simple dienes with S{sub 2}O have been reported. However, there were no reports of direct S{sub 2}O complex synthesis prior to our initial work. The authors recently published a synthesis of 4,5-diphenyl-3,6-dihydro-1,2-dithiin 1-oxide (2) which liberates S{sub 2}O via a transition-metal-assisted retro-Diels-Alder reaction. Here we report further on the unusual reactivity of 2 and its utilization in the synthesis of cyclic thiosulfinate esters.

Spectral properties of condensed phases of disulfur monoxide, polysulfur oxide, and irradiated sulfur

Spectral reflectances of several compounds of interest for the interpretation of planetary observations have been measured over the range 200–1700 nm. These materials are disulfur monoxide (S 2O) and polysulfur oxide (PSO) condensates, which are dissociation products of sulfur dioxide, and of elemental sulfur irradiated with ultraviolet light and X-rays. S 2O is a dark red solid because of two strong bands at 420 and 530 nm, which are probably due to S 3 and S 4 chains resulting from partial thermal decomposition. PSO is a pale yellow solid that absorbs strongly in the UV, but has no bands in the visible or near IR. Its low temperature spectrum is thermally stable and resembles that of elemental S at room temperature. The pressure above PSO is much lower than the vapor pressure of SO 2 at the same temperature. Elemental S has strong bands in the UV. It is normally white at low temperature, but irradiation by UV light causes it to turn yellow, evidently because of the broadening of the short-wavelength absorption bands. Irradiation of S by X-rays produces an orange color by creation of a band at 460 nm.

ChemInform Abstract: Novel Synthetic Routes to Disulfur and Disulfur Monoxide Ligands: Nucleophilic Attack at Coordinated Imino‐oxo‐λ4‐sulfanes.

AbstractThe reactions of (I) and (V) with (II) lead almost quantitatively to (III) and (VI) which in turn are hydrolyzed to the corresponding sulfur dioxide complexes.

ChemInform Abstract: Synthesis of a Stable Disulfur Monoxide Precursor and Trapping of Disulfur Monoxide with Transition‐Metal Complexes.

AbstractThe air‐stable, crystalline title precursor compound (VI) is prepared in a total yield of 30% (see scheme).

Additions and Corrections - Synthesis of a stable disulfur monoxide precursor and trapping of disulfur monoxide with transition-metal complexes [Erratum to document cited in CA108(19):167673G

Additions and Corrections - Synthesis of a stable disulfur monoxide precursor and trapping of disulfur monoxide with transition-metal complexes [Erratum to document cited in CA108(19):167673G

Synthesis of a stable disulfur monoxide precursor and trapping of disulfur monoxide with transition-metal complexes

A partir d'anhydride diphenylmaleique, via la reaction du thiosulfate de sodium et de dibromo-1,4 diphenyl-2,3 butene-2, synthese d'oxyde-1 de dihydro-3,6 diphenyl-4,5 dithiinne-1,2; traitement de ce compose par (CH 3 ) n CpMn(CO) 2 (THF) (n=1 ou 5) et formation d'un complexe η 2 -S 2 O

The equilibrium structure of disulfur monoxide: Diode laser spectroscopy of ν1 and ν3 of S 218O and ν3 of S 216O

Diode laser spectroscopy of ν 1 and ν 3 of 32S 2 18O and ν 3 of 32S 2 16O has been carried out and several hundred transition frequencies were measured with a nominal accuracy of ±0.001 cm −1. These data have been combined with earlier microwave and diode laser measurements to produce accurate rotational and distortion constants for the (0, 0, 0), (1, 0, 0), and (0, 0, 1) vibrational states of both isotopic species. These results were combined with microwave data from (0, 1, 0) of both isotopes to allow and equilibrium structure for S 2O to be calculated.

Untersuchungen zur oxidation des dischwefel-liganden in (η 5-C 5Me 5)M(CO) 2S 2 (M = Mn, Re)

The halfsandwich compounds (Cp *M(CO) 2S 2 (M = Mn or Re) are oxidized by 3-chloro-perbenzoic acid at the disulfur ligand to give disulfur monoxide complexes, Cp *M(CO) 2S 2O 1 1 Abkürzungen: Cp = η 5-cyclopentadienyl, η 5-C 5H 5; Cp * = η 5-pentamethylcyclopentadienyl, η 5-C 5Me 5; diphos = 1,2-Bis(diphenylphosphino)ethan, Ph 2PCH 2CH 2PPh 2. Further oxidation leads to Cp *M(CO) 2S 2O 2. A comparison of the carbonyl stretching frequencies, ν(CO), and derived force constants, k(CO), indicates that sulfur-containing ligands (S 2, SO, SO 2, S 2O, S 2O 2) are stronger electron-withdrawing groups than the ligand cation monoxide, CO. The acceptor capacity increases in the order S 2 < S 2O < S 2O 2.

The rs structure of disulfur monoxide: The microwave spectrum of S218O

In a novel flow system 95 at.% enriched S 2 18 O was produced and the microwave spectrum in the states (0, 0, 0) and (0, 1, 0) was observed. The resulting constants together with the data already published allowed the complete r s structure of S 2 O to be determined.

Disulfur Monoxide as Complex Ligand—Preparation and Molecular Structure of [(η5‐C5Me5)Mn(CO)2(S2O)

Disulfur Monoxide as Complex Ligand—Preparation and Molecular Structure of [(η⁵‐C₅Me₅)Mn(CO)₂(S₂O)

The Mechanisms of Thionyl Chloride Reduction at Solid Electrodes

An experimental technique has been devised which allows in situ sampling of electrolyte from a functioning cell, followed by rapid FTIR analysis for soluble reaction products. Disulfur monoxide is observed as an intermediate discharge product. The half‐life of is estimated to be about 20 min. The presence of is consistent with sulfur chemistry, as well as the accepted stoichiometry of the battery system. A possible safety hazard for low temperature discharges of cells is identified.

ChemInform Abstract: EXCITATION AND FLUORESCENCE SPECTRA OF DISULFUR MONOXIDE

Chemischer InformationsdienstVolume 13, Issue 52 Physical Inorganic Chemistry ChemInform Abstract: EXCITATION AND FLUORESCENCE SPECTRA OF DISULFUR MONOXIDE C. L. CHIU, Search for more papers by this authorP. C. SUNG, Search for more papers by this authorL. D. CHEN, Search for more papers by this author C. L. CHIU, Search for more papers by this authorP. C. SUNG, Search for more papers by this authorL. D. CHEN, Search for more papers by this author First published: December 28, 1982 https://doi.org/10.1002/chin.198252009AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume13, Issue52December 28, 1982 RelatedInformation

Excitation and fluorescence spectra of disulfur monoxide

Excitation and fluorescence spectra of the 3400-Å system of S 2O are reported for the first time at low resolution. Fluorescence quantum yields for the upper vibronic states are measured as a function of absorption peaks (bands). Because of the unusually small quantum yields of some absorption peaks and because of the broader bandwidths of some fluorescence bands, multiple transitions are assumed to occur within each “single” absorption peak. Thirty-one fluorescence peaks are identified and grouped into five v″ 2 progressions. Although v″ 2 up to 8 was assigned, no new vibrational constants are derived because of the low spectral resolution.