Fluorothiazynes, 50 years old and still exciting: electrophilic attack at the thiazyl nitrogen of NSF2NS(O)F2

Mews, Rüdiger; Borrmann, Tobias; Hoppenheit, R.; Lork, Enno; Parsons, Simon; Petersen, Jan; Schröter, M.; Stohrer, Wolf‐Dieter; Waterfeld, Alfred; Watson, Paul G.

doi:10.1016/j.jfluchem.2004.09.023

Cited by 6 publications

(4 citation statements)

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“…The free ligands {N(Ph 2 SN)(Ph 2 SNH)} (1) was synthesized as described previously [7]. (4). A solution of 1 (166 mg, 0.4 mmol) and sodium methoxide (22 mg, 0.4 mmol) in methanol (1.0 mL) was slowly added to a solution of CuCl 2 (81 mg, 0.6 mmol or 41 mg, 0.4 mmol) in the same solvent (1.0 mL) at ambient temperature, which started to precipitate a solid within 1 minute.…”

Section: Synthesesmentioning

confidence: 99%

“…Mews et al prepared trifluoro-λ 6 -sulfanenitrile (F 3 S≡N) and its derivatives (F 2 RS≡N, e.g., R = Me 2 N-, F 2 (O=)S=N-), and investigated their metal coordination chemistry [1][2][3]. Recently, we prepared fluoro(diphenyl)-λ 6 -sulfanenitrile (Ph 2 FS≡N) and reported the formation of the various substituted λ 6 -sulfanenitriles [4][5][6][7][8][9][10][11][12][13][14]. Among them, new types of λ 6 -sulfanenitrile with nitrilo and imino groups (type A) or two nitrilo groups (ndsdsd, type B) at both ends have been shown to complexes as bidentate N,N' ligands.…”

Section: Introductionmentioning

confidence: 99%

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Syntheses and Crystal Structures of and

Fujii

Kanno

Hirata

2010

International Journal of Inorganic Chemistry

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Section: Synthesesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Syntheses and Crystal Structures of and

Fujii

Kanno

Hirata

2010

International Journal of Inorganic Chemistry

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“…Its presence was inferred by the precipitation of [P(C 6 H 5 ) 4 ][NSOF 2 ], with subsequent hydrolyses leading to nonisolable H 2 NSO 2 F, H 2 NSO 3 H, and [NH 4 ][HSO 4 ] . These and other nucleophilic substitution reactions with NSF 3 form the basis for a significant body of work in the field of sulfur-nitrogen-fluorine chemistry. ,, Products of nucleophilic substitution at sulfur that retain the formal NS triple bond are generated when NSF 3 reacts with secondary amines or alcohols, perfluoroalkylating reagents , or organolithium reagents …”

Section: Introductionmentioning

confidence: 99%

“…26 These and other nucleophilic substitution reactions with NtSF 3 form the basis for a significant body of work in the field of sulfur-nitrogen-fluorine chemistry. 5,15,27 Products of nucleophilic substitution at sulfur that retain the formal NtS triple bond are generated when NtSF 3 reacts with secondary amines 28 or alcohols, 29 perfluoroalkylating reagents 30,31 or organolithium reagents. 32 In recent years, a new role has emerged for NtSF 3 as a synthon for XeÀN bond formation.…”

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confidence: 99%

Ennobling an Old Molecule: Thiazyl Trifluoride (N≡SF₃), a Versatile Synthon for Xe–N Bond Formation

2011

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The fields of sulfur-nitrogen-fluorine chemistry and noble-gas chemistry have been significantly extended by the syntheses and characterizations of four new Xe-N-bonded cations derived from N≡SF(3). The adduct-cation, F(3)S≡NXeF(+), has provided the entry point to a significant chemistry through HF solvolysis of the coordinated N≡SF(3) ligand and HF-catalyzed and solid-state rearrangements of F(3)S≡NXeF(+). The HF solvolyses of [F(3)S≡NXeF][AsF(6)] in anhydrous HF (aHF) and aHF/BrF(5) solutions yield the F(4)S═NXe(+) cation, which likely arises from an HF-catalyzed mechanism. The F(4)S═NXe(+) cation, in turn, undergoes HF displacement to form F(4)S═NH(2)(+) and XeF(2), as well as HF addition to the S═N bond to form F(5)SN(H)Xe(+). Both cations undergo further solvolyses in aHF to form the F(5)SNH(3)(+) cation. The F(4)S═NXe(+) and F(4)S═NH(2)(+) cations were characterized by NMR spectroscopy and single-crystal X-ray diffraction and exhibit high barriers to rotation about their S═N double bonds. They are the first cations known to contain the F(4)S═N- group and significantly extend the chemistry of this ligand. The solid-state rearrangement of [F(3)S≡NXeF][AsF(6)] at 22 °C has yielded [F(4)S═NXe][AsF(6)], which was characterized by Raman spectroscopy, providing the first examples of xenon bonded to an imido nitrogen and of the F(4)S═N- group bonded to a noble-gas element. The rearrangement of [F(3)S≡NXeF][AsF(6)] in a N≡SF(3) solution at 0 °C also yielded [F(4)S═NXe−N≡SF(3)][AsF(6)], which represents a rare example of a N−Xe−N linkage and the first to be characterized by X-ray crystallography. Solvolysis of N≡SF(3) in aHF was previously shown to give the primary amine F(5)SNH(2), whereas solvolysis in the superacid medium, AsF(5)/aHF, results in amine protonation to give [F(5)SNH(3)][AsF(6)]. Complete structural characterizations were not available for either species. Isolation of F(5)SNH(2)·nHF from the reaction of N≡SF(3) with HF has provided a structural characterization of F(5)SNH(2) by Raman spectroscopy. Crystal growth by sublimation of F(5)SNH(2)·nHF at -30 to -40 °C has resulted in the X-ray crystal structure of F(5)SNH(2)·2[F(5)SNH(3)][HF(2)]·4HF and structural characterizations of F(5)SNH(2) and F(5)SNH(3)(+). The redox decomposition of [F(4)S═NXe−N≡SF(3)][AsF(6)] in N≡SF(3) at 0 °C generated Xe, cis-N(2)F(2), and [F(3)S(N≡SF(3))(2)][AsF(6)].

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Synthesis and characterization of Co(II), Ni(II), and Cu(II) complexes containing an eight-membered disulfanenitrile chelating ring

Fujii

Kanno

Hirata

et al. 2008

Inorganica Chimica Acta

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Fluorothiazynes, 50 years old and still exciting: electrophilic attack at the thiazyl nitrogen of NSF2NS(O)F2

Cited by 6 publications

References 37 publications

Syntheses and Crystal Structures of and

Syntheses and Crystal Structures of and

Ennobling an Old Molecule: Thiazyl Trifluoride (N≡SF₃), a Versatile Synthon for Xe–N Bond Formation

Synthesis and characterization of Co(II), Ni(II), and Cu(II) complexes containing an eight-membered disulfanenitrile chelating ring

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Fluorothiazynes, 50 years old and still exciting: electrophilic attack at the thiazyl nitrogen of NSF2NS(O)F2

Cited by 6 publications

References 37 publications

Syntheses and Crystal Structures of and

Syntheses and Crystal Structures of and

Ennobling an Old Molecule: Thiazyl Trifluoride (N≡SF3), a Versatile Synthon for Xe–N Bond Formation

Synthesis and characterization of Co(II), Ni(II), and Cu(II) complexes containing an eight-membered disulfanenitrile chelating ring

Contact Info

Product

Resources

About

Ennobling an Old Molecule: Thiazyl Trifluoride (N≡SF₃), a Versatile Synthon for Xe–N Bond Formation