Bis[bis(pentafluor‐λ
 6
 ‐sulfanyl)amino]quecksilber, Hg[N(SF
 5
 )
 2
 ]
 2

Waterfeld, Alfred; Mews, Rüdiger

doi:10.1002/cber.19831160442

Cited by 10 publications

(1 citation statement)

References 13 publications

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“…Species containing the F 4 SN-group are presently limited to the neutral molecules F 4 SNL (L = F, − CH 3 , − CH 2 CH 3 , CF 3 , − CF 2 CF 3 , SF 5 , − SO 2 F, , and C(O)N(CH 2 CH 3 ) 2 ) and F 4 SN· . The majority have been characterized by vibrational ,,,,,,, and NMR ,− ,− ,, spectroscopy, and a number have been characterized by electron diffraction , and microwave spectroscopy. , …”

Section: Introductionmentioning

confidence: 99%

Solid-State and Solution Rearrangements of F₃S≡NXeF⁺Leading to the F₄S═NXe⁺Cation; Syntheses, HF Solvolyses, and Structural Characterizations of [F₄S═NXe][AsF₆] and [F₄S═NH₂][AsF₆]

2009

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The salt, [F(4)S=NXe][AsF(6)], has been synthesized by the solid-state rearrangement of [F(3)S[triple bond]NXeF][AsF(6)] and by HF-catalyzed rearrangement of [F(3)S[triple bond]NXeF][AsF(6)] in anhydrous HF (aHF) and HF/BrF(5) solvents. The F(4)S=NXe(+) cation undergoes HF solvolysis to form F(4)S=NH(2)(+), XeF(2), and the recently reported F(5)SN(H)Xe(+) cation. Both [F(4)S=NXe][AsF(6)] and [F(4)S=NH(2)][AsF(6)] have been characterized by (129)Xe and (19)F NMR spectroscopy in aHF and HF/BrF(5) solvents and by single-crystal X-ray diffraction. The [F(4)S=NXe][AsF(6)] salt was also characterized by Raman spectroscopy. The Xe-N bond of F(4)S=NXe(+) is among the shortest Xe-N bonds presently known (2.084(3) A), and the cation interacts with the AsF(6)(-) anion by means of a Xe---F-As bridge in which the Xe---F distance (2.618(2) A) is significantly less than the sum of the Xe and F van der Waals radii. Both F(4)S=NXe(+) and F(4)S=NH(2)(+) exhibit trigonal bipyramidal geometries about sulfur, with nitrogen in the equatorial plane and the nitrogen substituents coplanar with the axial fluorine ligands of sulfur. The F(4)S=NH(2)(+) cation is isoelectronic with F(4)S=CH(2) and, like F(4)S=CH(2), has a high barrier to rotation about the S=N double bond and to pseudorotation of the trigonal bipyramidal F(4)S=N- moiety. The solution and solid-state rearrangements of F(3)S[triple bond]NXeF(+) to F(4)S=NXe(+) are proposed to result from attack at sulfur by fluoride ion arising from HF in solution and from the AsF(6)(-) anion in the solid state. Quantum-chemical calculations were employed to calculate the gas-phase geometries, charges, bond orders, valencies, and vibrational frequencies of F(4)S=NXe(+) and F(4)S=NH(2)(+). The F(4)S=NXe(+) cation provides the first example of xenon bonded to an imido-nitrogen, and together with the F(4)S=NH(2)(+) cation are presently the only cations known to contain the F(4)S=N-group. Both cations are intermediates in the HF solvolysis pathways of F(3)S[triple bond]NXeF(+) which lead to F(5)SN(H)Xe(+) and F(5)SNH(3)(+), and significantly extend the chemistry of the F(4)S=N-group.

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Section: Introductionmentioning

confidence: 99%

Solid-State and Solution Rearrangements of F₃S≡NXeF⁺Leading to the F₄S═NXe⁺Cation; Syntheses, HF Solvolyses, and Structural Characterizations of [F₄S═NXe][AsF₆] and [F₄S═NH₂][AsF₆]

2009

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Cesium, Mercury, and Silver Salts with Sulfur–Nitrogen–Fluorine Anions: Useful Transfer Reagents for NSF Building Blocks

Mews

2012

Efficient Preparations of Fluorine Compounds

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ChemInform Abstract: BIS(BIS(PENTAFLUORO‐Λ6‐SULFANYL)AMIDO)MERCURY, HG(N(SF5)2)2

Waterfeld¹,

Mews²

1983

Chemischer Informationsdienst

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Bis[bis(pentafluor‐λ ⁶ ‐sulfanyl)amino]quecksilber, Hg[N(SF ₅ ) ₂ ] ₂

Abstract: Bis[bis(pentafluoro-h6-sulfanyl)amino]mercury, Hg[N(SF&12

Cited by 10 publications

References 13 publications

Solid-State and Solution Rearrangements of F₃S≡NXeF⁺Leading to the F₄S═NXe⁺Cation; Syntheses, HF Solvolyses, and Structural Characterizations of [F₄S═NXe][AsF₆] and [F₄S═NH₂][AsF₆]

Solid-State and Solution Rearrangements of F₃S≡NXeF⁺Leading to the F₄S═NXe⁺Cation; Syntheses, HF Solvolyses, and Structural Characterizations of [F₄S═NXe][AsF₆] and [F₄S═NH₂][AsF₆]

Cesium, Mercury, and Silver Salts with Sulfur–Nitrogen–Fluorine Anions: Useful Transfer Reagents for NSF Building Blocks

ChemInform Abstract: BIS(BIS(PENTAFLUORO‐Λ6‐SULFANYL)AMIDO)MERCURY, HG(N(SF5)2)2

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Bis[bis(pentafluor‐λ 6 ‐sulfanyl)amino]quecksilber, Hg[N(SF 5 ) 2 ] 2

Abstract: Bis[bis(pentafluoro-h6-sulfanyl)amino]mercury, Hg[N(SF&12

Cited by 10 publications

References 13 publications

Solid-State and Solution Rearrangements of F3S≡NXeF+Leading to the F4S═NXe+Cation; Syntheses, HF Solvolyses, and Structural Characterizations of [F4S═NXe][AsF6] and [F4S═NH2][AsF6]

Solid-State and Solution Rearrangements of F3S≡NXeF+Leading to the F4S═NXe+Cation; Syntheses, HF Solvolyses, and Structural Characterizations of [F4S═NXe][AsF6] and [F4S═NH2][AsF6]

Cesium, Mercury, and Silver Salts with Sulfur–Nitrogen–Fluorine Anions: Useful Transfer Reagents for NSF Building Blocks

ChemInform Abstract: BIS(BIS(PENTAFLUORO‐Λ6‐SULFANYL)AMIDO)MERCURY, HG(N(SF5)2)2

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Bis[bis(pentafluor‐λ ⁶ ‐sulfanyl)amino]quecksilber, Hg[N(SF ₅ ) ₂ ] ₂

Solid-State and Solution Rearrangements of F₃S≡NXeF⁺Leading to the F₄S═NXe⁺Cation; Syntheses, HF Solvolyses, and Structural Characterizations of [F₄S═NXe][AsF₆] and [F₄S═NH₂][AsF₆]

Solid-State and Solution Rearrangements of F₃S≡NXeF⁺Leading to the F₄S═NXe⁺Cation; Syntheses, HF Solvolyses, and Structural Characterizations of [F₄S═NXe][AsF₆] and [F₄S═NH₂][AsF₆]