Tricoordinate hypervalent sulfur compounds

Arduengo, Anthony J.; Burgess, Edward M.

doi:10.1021/ja00449a078

Cited by 84 publications

(45 citation statements)

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“…Conversely, bromination of 101a produced bromine analogues of 135 (X ϭ Br). [203] Compound 135b, the nominal adduct of 136 with SF 2 , was prepared by exchanging the chlorine atoms of 135a with fluorine. Reactions of 136 with SF 4 , SO 2 ClF, and SO 2 F 2 gave rise to 2-fluoroimidazolium salts rather than to adducts.…”

Section: Reverse Ylidesmentioning

confidence: 99%

Carbene Complexes of Nonmetals

Kirmse

2005

Eur J Org Chem

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Electrophilic carbenes accept a variety of n‐ and π‐donors. The products range from persistent ylides to matrix‐isolated xenon complexes. Ylides can be viewed as carbene complexes if they regenerate carbenes thermally or undergo concerted methylene transfer reactions. According to these definitions, the present review focuses on oxonium and iodonium ylides. Transient π‐complexes appear to be involved in addition reactions of carbenes with arenes (but not with alkenes). Nucleophilic carbenes form adducts with Lewis acids which are, for the most part, stable and have been well characterized structurally. Only recently attention has been directed to reversible systems. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Reverse Ylidesmentioning

confidence: 99%

Carbene Complexes of Nonmetals

Kirmse

2005

Eur J Org Chem

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“…Typical reactions of these imidazoline-2-thiones include S-alkylation [34 -36], addition of halogen [37,38], oxidative desulfurization [4,10,39,40], reduction to the carbene [41,42], and formation of metal complexes [43 -45]. Numerous crystal structures of 1,3-disubstituted imidazoline-2-thione complexes with Al, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Ru, Rh, Ag, Cd, In, Sb, Te, W, Re, Ir, Au, Hg, Pb, and Bi were found in the Cambridge Structural Database (version 5.33, August 2012).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Crystal Structures of New 1,3-Disubstituted Imidazoline-2-thiones

Laus

Kahlenberg

Wurst

et al. 2013

Zeitschrift Für Naturforschung B

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Two methods (MeOH/K 2 CO 3 , pyridine/Et 3 N) were assessed for the introduction of sulfur into the 2-position of 1,3-disubstituted quaternary imidazolium salts 1-9 (Cl, I, BF 4 , PF 6 , CH 3 OSO 3 were used as anions) to yield nine 1,3-disubstituted imidazoline-2-thiones 10-18 (1, 10: R 1 = CH 3 , R 2 = CH 3 ; 2, 11: R 1 = OCH 2 Ph, R 2 = CH 3 ; 3, 12: R 1 = OCH 3 , R 2 = CH 3 ; 4, 13: R 1 = OCH 3 , R 2 = OCH 3 ; 5, 14: R 1 = NH 2 , R 2 = CH 2 Ph; 6, 15: R 1 = NCHPh, R 2 = CH 3 ; 7, 16: R 1 = NH 2 , R 2 = CH 3 ; 8, 17: R 1 = NCHPh, R 2 = NCHPh; 9, 18: R 1 = NH 2 , R 2 = OCH 3 ). Compounds 11-18 represent N-alkyloxy and N-amino imidazoline-2-thiones, whereas 10 served as reference compound. The first method was advantageous for the conversion 1 → 10 due to faster reaction, whereas in the reaction 2 → 11 considerable amounts of by-products were formed. Pure thiones 11, 14, 16, 17, and 18 were obtained only by the second method. Both methods worked for the synthesis of the methoxy derivatives 12 and 13 from 3 and 4, and the benzylideneamino derivative 15 from 6. 1-Amino-3-methylimidazoline-2-thione (16) was also prepared by hydrolysis of the benzylideneamino derivative 15. Crystal structures of seven 1,3-disubstituted imidazoline-2-thiones were determined by singlecrystal X-ray diffraction. Intermolecular C-H···S contacts were identified and, additionally, N-H···S interactions in aminothiones 14 and 16. The 1 H NMR shifts of 10 and 13 were satisfactorily correlated with the Kamlet-Abboud-Taft π * and β parameters in ten solvents. From the lack of correlation with the α parameter and from the C=S bond length (average 1.68Å) a significant contribution of a mesoionic imidazolium-2-thiolate resonance structure seems unlikely.

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“…[2] An alternative synthetic method involves the oxidative addition of dihalogens, X 2 , to chalcogen-containing donor molecules. [3,4] For example, the addition of Cl 2 to 1,3-dimethylA C H T U N G T R E N N U N G imidazoline-2-thione [5] and of Br 2 to 1,3-dimethylimidazoline-2-selone [6] affords stable compounds featuring linear Cl À S À Cl and Br À Se À Br groups, respectively, that are perpendicular to the imidazoline ring. These products can also be formally regarded as adducts between 1,3-dimethyl-A C H T U N G T R E N N U N G imidazoline-2-ylidene and SCl 2 or SeBr 2 .…”

Section: Introductionmentioning

confidence: 99%

“…In fact, no "T-shaped" sulfur adducts with I 2 have so far been reported, whereas three with Br 2 have been structurally characterised. [5,14] On the other hand, analogous selenium adducts with Br 2 are numerous, [13,15] whereas only three examples with I 2 have been reported. [16] Hypervalent sulfur and selenium compounds containing the linear ClÀEÀCl (E = S, Se) group are very well known.…”

Section: Introductionmentioning

confidence: 99%

A Unique Case of Oxidative Addition of Interhalogens IX (X=Cl, Br) to Organodiselone Ligands: Nature of the Chemical Bonding in Asymmetric ISeX Polarised Hypervalent Systems

Juárez-Pérez

Aragoni

Arca

et al. 2011

Chemistry A European J

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The reactivity of the imidazoline-2-selone derivatives 1,1'-methylenebis(3-methyl-4-imidazoline-2-selone) (D1) and 1,2-ethylenebis(3-methyl-4-imidazoline-2-selone) (D2) towards the interhalogens IBr and ICl has been investigated in the solid state with the aim of synthesising "T-shaped" hypervalent chalcogen compounds featuring the extremely rare linear asymmetric I-E-X moieties (E=S, Se; X=Br, Cl). X-ray diffraction analysis and FT-Raman measurements provided a clear indication of the presence in the compounds obtained of discrete molecular adducts containing I-Se-Br and I-Se-Cl hypervalent moieties following a unique oxidative addition of interhalogens IX (X=Cl, Br) to the organoselone ligands. In all asymmetric hypervalent systems isolated, a strong polarisation was observed, with longer bond lengths at the selenium atom involving the most electronegative halogen. A topological electron density analysis on model compounds based on the quantum theory of atoms-in-molecules (QTAIM) and electron localisation function (ELF) established the three-centre-four-electron (3c-4e) nature of the bonding in these very polarised selenium hypervalent systems and new criteria were suggested to define and ascertain the hypervalency of the selenium atoms in these and related halogen and interhalogen adducts.

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Tricoordinate hypervalent sulfur compounds

Cited by 84 publications

References 0 publications

Carbene Complexes of Nonmetals

Carbene Complexes of Nonmetals

Synthesis and Crystal Structures of New 1,3-Disubstituted Imidazoline-2-thiones

A Unique Case of Oxidative Addition of Interhalogens IX (X=Cl, Br) to Organodiselone Ligands: Nature of the Chemical Bonding in Asymmetric ISeX Polarised Hypervalent Systems

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