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Revision as of 12:57, 10 January 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 450808533 of page Thiazyl_fluoride for the Chem/Drugbox validation project (updated: 'CASNo').  Latest revision as of 17:12, 5 November 2024 edit Citation bot (talk | contribs)Bots5,391,744 edits Misc citation tidying. | Use this bot. Report bugs. | #UCB_CommandLine 
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}}
{{chembox {{chembox
| Verifiedfields = changed
⚫ | verifiedrevid = 401630817
| Watchedfields = changed
⚫ | verifiedrevid = 470606393
| ImageFile = Thiazyl-fluoride-2D-dimensions.png | ImageFile = Thiazyl-fluoride-2D-dimensions.png
| ImageSize = | ImageSize =
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| IUPACName = | IUPACName =
| OtherNames = | OtherNames =
| Section1 = {{Chembox Identifiers |Section1={{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 123854 | ChemSpiderID = 123854
| InChI = 1/FNS/c1-3-2 | InChI = 1/FNS/c1-3-2
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} | StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = IMFUYZDKLVTPSW-UHFFFAOYSA-N | StdInChIKey = IMFUYZDKLVTPSW-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|changed|??}}
| CASNo = <!-- blanked - oldvalue: 18820-63-8 -->
| PubChem = 140430 | CASNo = 18820-63-8
| SMILES = FS#N | PubChem = 140430
| SMILES = FS#N
}} }}
| Section2 = {{Chembox Properties |Section2={{Chembox Properties
| Formula = NSF | Formula = NSF
| MolarMass = 65.07 g mol<sup>−1</sup> | MolarMass = 65.07 g mol<sup>−1</sup>
| Appearance = colourless gas | Appearance = colourless gas
| Density = | Density =
| MeltingPt = −89 °C | MeltingPtC = −89
| BoilingPt = 0.4 °C | BoilingPtC = 0.4
| Solubility = | Solubility =
}} }}
}} }}

'''Thiazyl fluoride''', NSF, is a colourless, pungent gas at room temperature and condenses to a pale yellow liquid at 0.4 '''°'''C.<ref name=":0">{{cite journal | author = Oskar Glemser and Rüdiger Mews | title = Chemistry of Thiazyl Fluoride (NSF) and Thiazyl Trifluoride (NSF<sub>3</sub>): A Quarter Century of Sulfur-Nitrogen-Fluorine Chemistry | year = 1980 | journal = ] | volume = 19 | issue = 11 | pages = 883–899 | doi = 10.1002/anie.198008831}}</ref> Along with ], NSF<sub>3</sub>, it is an important precursor to sulfur-nitrogen-fluorine compounds. It is notable for its extreme ].

== Synthesis ==
Thiazyl fluoride can be synthesized by various methods, such as ] of ] with ] or ]. It can be purified by vacuum distillation.<ref>{{Cite journal |last=Fischer |first=Gad |date=1974-05-01 |title=Vibrational assignments in the electronic spectra of thiazyl fluoride |url=https://dx.doi.org/10.1016/0022-2852%2874%2990050-2 |journal=Journal of Molecular Spectroscopy |language=en |volume=51 |issue=2 |pages=208–215 |doi=10.1016/0022-2852(74)90050-2 |bibcode=1974JMoSp..51..208F |issn=0022-2852}}</ref><ref>{{Cite journal |last1=Glemser |first1=Oskar |last2=Schröder |first2=Hans |last3=Haeseler |first3=Harke |date=1955-01-01 |title=Über Schwefel-Stickstoff-Fluorverbindungen |url=https://doi.org/10.1007/BF00621536 |journal=Naturwissenschaften |language=de |volume=42 |issue=2 |pages=44 |doi=10.1007/BF00621536 |bibcode=1955NW.....42...44G |s2cid=32868758 |issn=1432-1904}}</ref> However, because this synthetic pathway yields numerous side-products, an alternative approach is the reaction of imino(triphenyl)phosphines with ] by cleavage of the bond to form sulfur difluoride imides and triphenyldifluorophosphorane.<ref>{{Cite journal |last1=Appel |first1=Rolf |last2=Laßmann |first2=Eberhard |date=July 1971 |title=Über eine neue Synthese des Thiazylfluorids, NSF |url=https://onlinelibrary.wiley.com/doi/10.1002/cber.19711040727 |journal=Chemische Berichte |language=en |volume=104 |issue=7 |pages=2246–2249 |doi=10.1002/cber.19711040727 |issn=0009-2940}}</ref> These products readily decompose yielding thiazyl fluoride.

For synthesis on a preparative scale, the decomposition of compounds already containing the moiety is commonly used:<ref name=Sulf>{{cite book|title=Sulfur in Organic and Inorganic Chemistry|volume=1|editor-first=Alexander|editor-last=Senning|year=1971|publisher=Marcel Dekker|location=New York|lccn=70-154612|isbn=0-8247-1615-9|first=H.&nbsp;W.|last=Roesky|chapter=The Sulfur&ndash;Nitrogen Bond|page=22}}</ref>
]

== Reactivity ==
=== Reactions with electrophiles and Lewis acids===
] remove fluoride to afford thiazyl salts:<ref>{{Cite journal |last=Mews |first=Rüdiger |date=November 1976 |title=Das Thionitrosylkation NS+ als Synthesereagens |url=https://onlinelibrary.wiley.com/doi/10.1002/ange.19760882205 |journal=Angewandte Chemie |language=de |volume=88 |issue=22 |pages=757–758 |doi=10.1002/ange.19760882205|bibcode=1976AngCh..88..757M }}</ref>
:{{chem2|NSF + BF3 -> BF4}}

Thiazyl fluoride functions as a ] in {{chem2|+}}.<ref name=":0" /> and {{chem2|(2+)}} (M = Co, Ni). In all of its complexes, NSF is bound to the metal center through nitrogen.<ref name=":02">{{cite journal |author=Oskar Glemser and Rüdiger Mews |year=1980 |title=Chemistry of Thiazyl Fluoride (NSF) and Thiazyl Trifluoride (NSF<sub>3</sub>): A Quarter Century of Sulfur-Nitrogen-Fluorine Chemistry |journal=] |volume=19 |issue=11 |pages=883–899 |doi=10.1002/anie.198008831}}</ref>

=== Reactions with nucleophiles ===
Thiazyl fluoride reacts violently with water:<ref>{{Citation |last1=Mews |first1=Rudiger |title=Acyclic Sulfur Nitrogen Fluorine Compounds |date=2007-01-05 |url=https://onlinelibrary.wiley.com/doi/10.1002/9780470132555.ch6 |work=Inorganic Syntheses |pages=12–17 |editor-last=Shreeve |editor-first=Jean'ne M. |place=Hoboken, NJ, USA |publisher=John Wiley & Sons, Inc. |doi=10.1002/9780470132555.ch6 |isbn=978-0-470-13255-5 |access-date=2022-12-15 |last2=Keller |first2=Klaus |last3=Glemser |first3=Oskar |last4=Seppelt |first4=K. |last5=Thrasher |first5=J.}}</ref>
:{{chem2|NSF + 2 H2O -> SO2 + HF + NH3}}

]

] attack on thiazyl fluoride occurs at sulfur atom:.<ref>{{Cite journal |last1=Cohen |first1=B. |last2=Hooper |first2=T. R. |last3=Hugill |first3=D. |last4=Peacock |first4=R. D. |date=August 1965 |title=Preparation of Thiazyl Fluorides |url=https://www.nature.com/articles/207748b0 |journal=Nature |language=en |volume=207 |issue=4998 |pages=748–749 |doi=10.1038/207748b0 |bibcode=1965Natur.207..748C |s2cid=4163539 |issn=1476-4687}}</ref>
:{{chem2|NS\sF + Nu- -> NS\sNu + F-}}
Fluoride gives an adduct:
:{{chem2|NS\sF + F- -> NSF2-}}

The halogen derivatives XNSF<sub>2</sub> (X = F, Cl, Br, I) can be synthesized from reacting Hg(NSF)<sub>2</sub> with X<sub>2</sub>; whereby, ClNSF<sub>2</sub> is the most stable compound observed in this series.<ref>{{Cite journal |last1=Glemser |first1=Oskar |last2=Mews |first2=Rüdiger |last3=Roesky |first3=Herbert W. |date=May 1969 |title=Darstellung und Eigenschaften von Quecksilber-bis-schwefeldifluoridimid, N -Chlor-schwefeldifluoridimid und N -Brom-schwefeldifluoridimid |url=https://onlinelibrary.wiley.com/doi/10.1002/cber.19691020513 |journal=Chemische Berichte |language=en |volume=102 |issue=5 |pages=1523–1528 |doi=10.1002/cber.19691020513 |issn=0009-2940}}</ref>

=== Oligomerization and cycloaddition ===
At room temperature, thiazyl fluoride undergoes cyclic ] via the <chem>N-S</chem> multiple bonding:

:]

1,3,5-trifluoro-1<math>\lambda^4</math>,3<math>\lambda^4</math>,5<math>\lambda^4</math>,2,4,6-trithiatriazine is the yielded cyclic trimer, where each sulfur atom remains ].

Thiazyl fluoride also reacts via exothermic ] in the presence of dienes.

:]

== Structure and bonding ==
]
The N−S bond length is 1.448 Å, which is short, indicating multiple bonding, and can be represented by the following resonance structures:

:]

The NSF molecule has 18 total valence electrons and is isoelectronic to ]. Thiazyl fluoride adopts C<sub>s</sub>-symmetry and has been shown by isotopic substitution to be bent in the ground state.<ref>{{Cite journal |last1=So |first1=Suk Ping |last2=Richards |first2=W. Graham |date=1978-01-01 |title=Geometries and stabilities of NSF and SNF |url=https://pubs.rsc.org/en/content/articlelanding/1978/f2/f29787401743 |journal=Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics |language=en |volume=74 |pages=1743–1745 |doi=10.1039/F29787401743 |issn=0300-9238}}</ref><ref>{{Cite journal |last1=Dixon |first1=R. N. |last2=Duxbury |first2=G. |last3=Fleming |first3=G. R. |last4=Hugo |first4=J. M. V. |date=1972-05-01 |title=The photoelectron spectrum of thiazyl fluoride |url=https://dx.doi.org/10.1016/0009-2614%2872%2987141-0 |journal=Chemical Physics Letters |language=en |volume=14 |issue=1 |pages=60–63 |doi=10.1016/0009-2614(72)87141-0 |bibcode=1972CPL....14...60D |issn=0009-2614}}</ref> A combination of rotational analysis with Franck-Condon calculations has been applied to study the electronic excitation from the A<nowiki>''</nowiki><math>-</math>A' states, which results in the elongation of the <chem>N-S</chem> bond by 0.11 Å and a decrease in the <math>\measuredangle</math>NSF by 15.3<math>^\circ</math>.

== References ==
{{reflist}}

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