thiazyl fluoride

Thiazyl fluoride can be synthesized by various methods, such as fluorination of tetrasulfur tetranitride with silver(II) fluoride or mercuric fluoride. It can be purified by vacuum distillation.{{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|url-access=subscription }}{{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|url-access=subscription }} However, because this synthetic pathway yields numerous side-products, an alternative approach is the reaction of imino(triphenyl)phosphines with sulfur tetrafluoride by cleavage of the bond to form sulfur difluoride imides and triphenyldifluorophosphorane.{{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|url-access=subscription }} These products readily decompose yielding thiazyl fluoride.

For synthesis on a preparative scale, the decomposition of compounds already containing the moiety is commonly used:{{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. W.|last=Roesky|chapter=The Sulfur–Nitrogen Bond|page=22}}

:File:Thiazyl fluoride decomposition syntheses.webp{{clear-left}}

Lewis acids remove fluoride to afford thiazyl salts:{{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|url-access=subscription }}

:{{chem2|NSF + BF3 → [N\tS]+[BF4]-}}

Thiazyl fluoride functions as a ligand in {{chem2|[Re(CO)5NSF]+}}. and {{chem2|[M(NSF)6](2+)}} (M = Co, Ni). In all of its complexes, NSF is bound to the metal center through nitrogen.{{cite journal |author=Oskar Glemser and Rüdiger Mews |year=1980 |title=Chemistry of Thiazyl Fluoride (NSF) and Thiazyl Trifluoride (NSF₃): A Quarter Century of Sulfur-Nitrogen-Fluorine Chemistry |journal=Angew. Chem. Int. Ed. Engl. |volume=19 |issue=11 |pages=883–899 |doi=10.1002/anie.198008831}}

Thiazyl fluoride reacts violently with water:{{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.|url-access=subscription }}

:{{chem2|NSF + 2 H2O -> SO2 + HF + NH3}}

File:NSF-AIM-v2.svg

Nucleophilic attack on thiazyl fluoride occurs at sulfur atom:.{{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|url-access=subscription }}

:{{chem2|NS\sF + Nu- -> NS\sNu + F-}}

Fluoride gives an adduct:

:{{chem2|NS\sF + F- -> NSF2-}}

The halogen derivatives {{chem2|X\sN\dSF2}} (X = F, Cl, Br, I) can be synthesized from reacting {{chem2|Hg(NSF)2}} with {{chem2|X2}}; whereby, {{chem2|ClNSF2}} is the most stable compound observed in this series.{{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|url-access=subscription }}

At room temperature, thiazyl fluoride undergoes cyclic trimerization via the N-S multiple bonding:

:File:NSF-trimerization.webp

1,3,5-trifluoro-1λ⁴,3λ⁴,5λ⁴-2,4,6-trithiatriazine is the yielded cyclic trimer, where each sulfur atom remains tetravalent.

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

:File:NSF-pi-rxn3.webp

File:Thiazyl fluoride frontier molecular orbitals.svg

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

:File:NSF Resonance-Lewis Structure2.webp

The NSF molecule has 18 total valence electrons and is isoelectronic to sulfur dioxide. Thiazyl fluoride adopts C_s-symmetry and has been shown by isotopic substitution to be bent in the ground state.{{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|url-access=subscription }}{{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|url-access=subscription }} A combination of rotational analysis with Franck-Condon calculations has been applied to study the electronic excitation from the A''$-$A' states, which results in the elongation of the nitrogen-sulfur bond by 0.11 Å and a decrease in the $\backslash measuredangle$NSF by 15.3$^\backslash circ$.

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Category:Fluorides

Category:Nonmetal halides

Category:Nitrides

Category:Thiohalides

Category:Sulfur–nitrogen compounds