13693-10-2Relevant articles and documents
F5SN(H)Xe+; a rare example of xenon bonded to sp 3-hybridized nitrogen; synthesis and structural characterization of [F5SN(H)Xe][AsF6]
Smith, Gregory L.,Mercier, Helene P. A.,Schrobilgen, Gary J.
, p. 4173 - 4184 (2008)
The salt [F5SN(H)Xe][AsF6] has been synthesized by the reaction of [F5SNH3][AsF6] with XeF 2 in anhydrous HF (aHF) and BrF5 solvents and by solvolysis of [F3S=NXeF][AsF6] in aHF. Both F 5SN(H)Xe+ and F5SNH3+ have been characterized by 129Xe, 19F, and 1H NMR spectroscopy in aHF (-20°C) and BrF5 (supercooled to -70°C). The yellow [F5SN(H)Xe][AsF6] salt was crystallized from aHF at -20°C and characterized by Raman spectroscopy at -45°C and by single-crystal X-ray diffraction at -173°C. The Xe-N bond length (2.069(4) A) of the F5SN(H)Xe+ cation is among the shortest Xe-N bonds presently known. The cation interacts with the AsF6- anion by means of a Xe...F-As bridge in which the Xe...F distance (2.634(3) A) is significantly less than the sum of the Xe and F van der Waals radii (3.63 A) and the AsF6 - anion is significantly distorted from Oh symmetry. The 19F and 129Xe NMR spectra established that the [F 5SN(H)Xe][AsF6] ion pair is dissociated in aHF and BrF5 solvents. The F5SN(H)Xe+ cation decomposes by HF solvolysis to F5SNH3+ and XeF 2, followed by solvolysis of F5SNH3+ to SF6 and NH4+. A minor decomposition channel leads to small quantities of F5SNF2. The colorless salt, [F5SNH3][AsF6], was synthesized by the HF solvolysis of F3S≡NAsF5 and was crystallized from aHF at -35°C. The salt was characterized by Raman spectroscopy at -160°C, and its unit cell parameters were determined by low-temperature X-ray diffraction. Electronic structure calculations using MP2 and DFT methods were used to calculate the gas-phase geometries, charges, bond orders, and valencies as well as the vibrational frequencies of F5SNH 3+ and F5SN(H)Xe+ and to aid in the assignment of their experimental vibrational frequencies. In addition to F 5TeN(H)Xe+, the F5SN(H)Xe+ cation provides the only other example of xenon bonded to an sp3-hybridized nitrogen center that has been synthesized and structurally characterized. These cations represent the strongest Xe-N bonds that are presently known.
Trifluoromethylthiodifluoramine
Stump Jr., Eugene C.,Padgett, Calvin D.
, p. 610 - 610 (2008/10/08)
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