Chivers T. - A Guide to Chalcogen-Nitrogen Chemistry (2005)(en)

contain the NSF group, e.g., FC(O)NSF2 (Eq. 8.1) or Hg(NSF2)2 (Eq. 8.2).2 It forms the cyclic trimer (NSF)3 at room temperature. A high yield synthesis of NSF from (NSCl)3 and KF in tetramethylsulfone at 80°C has been reported.3

Monomeric NSCl is formed as a greenish-yellow gas by heating the cyclic trimer (NSCl)3 under vacuum or in an inert gas stream.4 NSCl monomer may also be generated in solutions of (NSCl)3 in liquid SO2 at room temperature or in CCl4 at 70°C.5 It trimerizes in the condensed state. Self-consistent field calculations predict that (a) the dimers (NSX)2 (X= F, Cl) are thermodynamically unstable with respect to 2NSX and (b) the trimer (NSF)3 is stable compared to 3NSF.6 Monomeric thiazyl halides NSX (X = Cl, Br) have also been generated by the pyrolysis of [S4N3]X at 120°C (X = Cl) or 90°C (X = Br).7 This method has been used to produce NSX in an argon matrix at 15 K for the determination of infra-red spectra. The gas-phase structures of NSF8a and NSCl8b have been determined by microwave spectroscopy. They are bent molecules (<NSF = 117°, <NSCl = 118°)) with sulfur–nitrogen bond lengths of 1.448 and 1.450 Å, respectively, consistent with substantial triple bond character. The sulfur-halogen distances are 1.643 Å (X= F) and 2.161 Å (X = Cl). Ab initio molecular orbital calculations show that NSCl is 18.4 kcal mol-1 more stable than the hypothetical thionitrosyl chloride SNCl.9 The energy difference is reduced to 8.6 kcal mol-1 for the corresponding cation radicals; [ClNS]+• has been tentatively identified in the gas phase by mass spectrometric methods.9

Monomeric thiazyl halides can be stabilized by coordination to transition metals and a large number of such complexes are known (Section 7.5). In addition, NSX monomers undergo several types of reactions that can be classified as follows: (a) reactions involving the Œ– system of the NA6 ERQG E UHDFWLRQV DW WKH QLWURJHQ FHQWUH F nucleophilic substitution reactions (d) halide abstraction, and (e) halide addition. Examples of each type of behaviour are illustrated below.

Scheme 8.1 Cycloaddition reactions of NSF

(a)NSF undergoes cycloaddition with hexafluorobuta-1,3-butadiene to form a six-membered ring (Scheme 8.1).10

(b)There is no clear evidence for nitrene reactions of NSF. However, irradiation of excess thiazyl fluoride in the presence of hexafluoropropene generates sulfenylaziridines (Scheme 8.1).

(c)Nucleophilic replacement of the fluoride substituent in NSF usually results in a rearrangement with loss of the formal NA6 WULSOH ERQG )RU

example, hydrolysis of moisture-sensitive NSF results in replacement of F- by OH- and subsequent isomerization of thiazyl hydroxide to thionyl

imide HNSO (Eq. 8.3) which, in turn, is hydrolyzed to give sulfur oxoanions.11

(d) The reaction of NSF with strong fluoride ion acceptors, e.g., MF5 (M = As, Sb) in liquid SO2 was the first synthesis of [SN]+ salts (Eq. 8.4).12 Although other preparative routes to these important reagents have subsequently been developed (Section 5.3.1), the original method gives the salt in highest purity.

(e) The thiazyl halide monomers NSX also undergo nucleophilic addition with halide ions to give ternary anions of the type [NSX2]-. The [NSF2]- ion in Cs[NSF2] and [(Me2N)3S][NSF2] has been characterized by vibrational spectra.13 The [NSCl2]- anion, obtained by chloride addition to NSCl (generated from the cyclic trimer), has been isolated in salts with large counter-anions, e.g., [Ph4P]+ and [Me4N]+.14 The [NSCl2]- anion in the [(Ph3PN)2SCl]+ salt has a slightly distorted Cs structure with a very short S–N bond (1.44 Å) and two loosely bound chlorine atoms [d(S–Cl) = 2.42 Å]. The structure is best described by the resonance forms depicted in Scheme 8.2.

Scheme 8.2 Resonance structures of [NSCl2]-

Selenazyl halides NSeX have not been characterized either as monomers or cyclic oligomers. However, the monomeric ligand is stabilized in metal complexes of the type [Cl4M(NSeCl)]2 (M = Mo, W), which are obtained from the reactions of MoCl5 or WCl6 with Se4N4 in dichloromethane.15 The bonding features in the anion [Cl5W(NSeCl)]- are similar to those in NSCl complexes (Section 7.5) with a short W=N bond, a Se=N bond length of 1.77 Å, and a bond angle <NSeCl of ca. 92°.

8.3Thiazyl Trifluoride NSF3 and Haloiminosulfur Difluorides XNSF2 (X = F, Cl)

Thiazyl trifluoride, a colourless gas with a pungent odour, is prepared by the oxidative decomposition of FC(O)NSF2 with AgF2 (Eq. 8.5).16a NSF3 is kinetically very stable even in the liquid form. The chemical inertness of NSF3 resembles that of SF6. For example, it does not react with sodium metal below 200°C.1

144 A Guide to Chalcogen–Nitrogen Chemistry

FC(O)NSF2 + 2AgF2 : 16)3 + 2AgF + COF2 (8.5)

The structure of NSF3 (8.1) in the gas phase has been determined by microwave spectroscopy to be a distorted tetrahedron with C3v geometry and a SA1 ERQG OHQJWK RI Å, consistent with triple bond character.16b The bond angle <FSF is ca. 94° and the S–F distance is 1.55 Å indicating a much stronger bond than that in NSF [d(S–F) = 1.64 Å. The mixed halide derivatives XNSF2 (X = Cl, Br, I) are obtained by the reaction of Hg(NSF2)2 with halogens (Eq. 8.6).2 This reaction also gives rise to FNSF2, a structural isomer of NSF3.17 The chloro derivative ClNSF2 (8.2) has been shown by electron diffraction to have a cis arrangement of the lone pairs on the sulfur and nitrogen atoms.18 The S– N and S–F bond lengths are 1.48 and 1.60 Å, respectively. Selfconsistent field calculations on NSF2R molecules and their RNSF2 isomers predict that the former is more stable for R = F, whereas the latter structural arrangement is preferred for R = Me, CF3, consistent

with experimental observations. The isomer FNSF2 is less stable than NSF3 by 3.8 kcal mol-1.19

The reactions of NSF3 have been investigated in considerable detail. They can be classified under the following categories: (a) reactions with electrophiles (b) addition to the SN triple bond and (c) reactions with nucleophiles. Some examples of these different types of behaviour are discussed below.

(a) A variety of metal complexes with up to four NSF3 ligands coordinated to the M2+ centre have been characterized (Section 7.5). In a

similar fashion NSF3 forms N-bonded adducts with fluoro Lewis acids (Eq. 8.7).1 The SA1 DQG HVSHFLDOO\ WKH 6–F bond lengths are

significantly shortened upon adduct formation as revealed by the X-ray structure of F5AsÂ16)3.1 These structural changes have been attributed to rehybridization of the lone pair on nitrogen from primarily s to sp character upon complex formation and a cocomitant increase in Œ- bonding in the S–F bonds.

(A = BF3, AsF5, SbF5)

A different type of behaviour is observed with the chloro Lewis acid BCl3. With this reagent halogen exchange occurs to produce the acyclic cation [N(SCl)2]+, as the [BCl4]- salt, rather than NSCl3.20 Thiazyl

trichloride NSCl3 is predicted to be unstable with respect to NSCl + Cl2.19

A singular example of the oxidative addition of an S–F bond in NSF3 to an electrophilic metal centre has been reported in the formation of the thiadiazyl difluoride complex [Ir(CO)ClF(NSF2)(PPh3)2] (Scheme 7.3).21 Protonation of NSF3 by the superacid HSO3F/SbF5 produces the thermally unstable [HNSF3]+ cation.1 Similarly, alkylation of NSF3 with [RSO2][AsF6] (R = Me, Et) gives [RNSF3]+ cations, which can be isolated as stable salts in the presence of weakly nucleophilic anions, e.g., [MF6]- (M = As, Sb).22 The reaction of [MeNSF3]+ with sodium fluoride at elevated temperatures yields MeN=SF4 (8.3), which was shown by electron diffraction to have a distorted trigonal pyramidal

structure analogous to that of the isoelectronic molecule OSF4.1

(b) Polar species XF (X = H, Cl) add to the SA1 WULSOH ERQG 7KH reaction of NSF3 with an excess of HF results in a double addition to give the stable pentafluorosulfur amine H2NSF5 (Eq. 8.8),23a which has an extensive derivative chemistry involving the NH2 group.1 For

(c) The reaction of NSF3 with nucleophilic reagents such as secondary amines, alcohols or organolithium reagents results in the formation of monosubstituted products with retention of the NA6 ERQG (T 1, 23b Hydrolysis of the kinetically inert NSF3 molecule requires hot alkali and generates HNSOF2 as the initial product. The structure of HNSOF2 (8.4), as determined by microwave spectroscopy,24 shows the NH and SF2 groups to be in a cis arrangement with respect to the S=N bond, which has a bond length of 1.47 Å.

The reactions of NSF3 with the amido-lithium reagents LiN(SiMe3)R (R = tBu, SiMe3) results in an interesting rearrangement to produce the sulfur triimides S(NR)3, isoelectronic with SO3.25 The first sulfur triimide 8.5a (R = SiMe3) was obtained in this manner (Eq. 8.10). Bis(trimethylsilylimino)sulfur difluoride (Me3SiN)2SF2 is a by-product of this reaction. The X-ray structure of the tert-butyl derivative 8.5b reveals the anticipated trigonal planar arrangement of NtBu groups around the sulfur(VI) atom with S=N bond lengths of 1.51 Å.25a The oxidation of the [S(NtBu)3]2- dianion with halogens is a better synthesis of 8.5b (Section 10.5).

NSF3 + 2LiN(SiMe3)2 : 6 16L0H3)3 + 2LiF + Me3SiF (8.10)

8.4Acyclic Chalcogen-Nitrogen–Halogen Cations [N(ECl)2]+ (E = S, Se) and [N(SeCl2)2]+

The most straightforward route to the acyclic cation [N(SCl)2]+ (8.6a) is the reaction of [NS]+ with SCl2 (Eq. 8.11).26 Other preparative methods include the reactions of (a) (NSCl)3 with SCl2 in the presence of a metal chloride (e.g., AlCl3 or SbCl5) or AgAsF627 or (b) an [SCl3]+ salt with N(SiMe3)3 in CCl4.28 Dechlorination of 8.6a with SnCl2 produces the [NS2]+ cation (Section 5.3.2).

The reaction of N(SiMe3)3 with SeCl4 in boiling CH2Cl2 yields Se2NCl3 (8.7a), which reacts with GaCl3 to produce [N(SeCl)2][GaCl4] containing the selenium analogue 8.6b.29 The bromo derivative 8.7b is prepared in a similar manner from SeBr4 and N(SiMe3)3.30 The attempted preparation of [SeN]+ from the reaction of equimolar quantities of [SeCl3][AsF6] with N(SiMe3)3 in CFCl3 produced instead the novel cation [N(SeCl2)2]+ (8.8).31 Surprisingly, [SeCl3][SbCl6] reacts with N(SiMe3)3 in a different way to give the cation 8.6b which is isolated as the cis, cis isomer.32 The reagent [SeCl3][FeCl4] produces [N(SeCl)2]2[FeCl4] in which the cation 8.6b• has a cis, tran geometry.33

The structures of various salts of 8.6a have been determined by X-ray diffraction. The cation adopts a U-shaped (C2v) geometry with an <NSN bond angle of 150 ± 1° in the absence of strong cation-anion interactions. The S–N bond lengths are ca. 1.53 Å and the S–Cl distances are relatively short at 1.91-1.99 Å. The structures of 8.6a, 8.7a,b and 8.8 exhibit Se–N bond lengths that are substantially shorter than the single

bond value of 1.86 Å. Negative hyperconjugation [lone pair (N) : 1* (Se-Cl)] accounts for the short S–N and Se–N bond lengths in these cations32, 34 and, in the case of 8.6b´, explains the inequality of the Se–N distances.32 The Se–Cl bond distances of 2.14-2.17 Å found for the two cations 8.6b and 8.8 are normal for terminal Se–Cl bonds, while the long distances (2.52 and 2.68 Å) for the bridging Se–Cl bonds in the neutral molecule 8.7a suggest ionic character for this chlorine atom. This conclusion is supported by calculations of the Mulliken charge distributions in 8.6b and 8.7a.32

8.5 Tellurium–Nitrogen–Chlorides [Te4N2Cl8]2+ and Te11N6Cl26

There are no tellurium analogues of the chalcogen–nitrogen halides described in Sections 8.2 and 8.3. However, the dication [Te4N2Cl8]2+ (8.9) is obtained, as the [AsF6]- salt, from the reaction of TeCl4 with N(SiMe3)3 in a 2:1 molar ratio in acetonitrile.35 The formation of the four-membered Te2N2 ring in 8.9 provides an illustration of the facile self-association of multiply bonded TeN species (cf., 8.21a and Section 10.4.2). This dication is a dimer of the hypothetical tellurium(IV) imide [Cl3Te–N=TeCl]+, which is a structural isomer of [N(TeCl2)2]+ (the tellurium analogue of 8.8). The compound [Te11N6Cl26]Â&7H8 is isolated from the reaction of TeCl4 with N(SiMe3)3 in boiling toluene.36 Each half of this centrosymmetric dimer contains a [Te5N3Cl10]+ cation (8.10) and a [Te5N3Cl12]- anion linked to a TeCl4 molecule. A Te5N3 structural core is common to both the anion and cation in this complex structure. The structure of cation 8.10 is comprised of two [Cl3Te–N=TeCl]+ cations (cf., 8.9) bridged by a monomeric NTeCl unit and a chloride ion.

+

8.6Thiodithiazyl and Selenadiselenazyl Dichloride [E3N2Cl]Cl (E = S, Se)

The [S3N2Cl]+ cation (8.11a) is an important intermediate in the synthesis of other S–N compounds, e.g., (NSCl)3, [S4N3]+ , S4N4 and S3N2O.37 It is conveniently prepared by refluxing S2Cl2 with dry, finely ground ammonium chloride (Eq. 8.12).38 [S3N2Cl]Cl may also be prepared from urea and S2Cl2.39 The other halo derivatives, [S3N2Br]+ and [S3N2F]+, are obtained by treatment of [S3N2][AsF6] with Br2 and by cycloaddition of NSF to [S2N]+, respectively.40 The selenium analogue [Se3N2Cl]+ (8.11b) is prepared by the reduction of the acyclic cation 8.6b with Ph3Sb.41 The explosive and insoluble compound Se3N2Cl2, which also contains the cyclic cation 8.11b, is formed in the reaction of Se2Cl2 with trimethylsilyl azide in CH2Cl2 (Eq. 8.13).42 X-ray diffraction studies show that 8.11a, in the [FeCl4]- salt,43 and 8.11b, in the [SbCl6]- salt,44 consist of slightly puckered five-membered rings.

8.7 Cyclotrithiazyl Halides (NSX)3 (X = Cl, F)

A safe and convenient procedure for the preparation of (NSCl)3 (8.12a) is the chlorination of [S3N2Cl]Cl with either Cl2 or SO2Cl2 (Eq. 8.14).38,45

The moisture-sensitive, pale-yellow product may be recrystallized from CCl4 without decomposition provided that the temperature is kept below

50°C. The fluoride (NSF)3 (8.12b) can be made in high yield by stirring 8.12a with AgF2 in CCl4 at room temperature.46 Halogen exchange between 8.12a and Me3SiBr produces the polymer (NSBr0.4)x rather than (NSBr)3.47 The cyclotrithiazyl halides (NSX)3 (X = Br, I) are unknown. There are no selenium analogues of 8.12a or 8.12b.

3[S3N2Cl]Cl + 3SO2Cl2 : 16&O3 + 3SCl2 + 3SO2 (8.14)

The six-membered rings 8.12a and 8.12b adopt chair conformations with all three halogen atoms in axial positions. This arrangement is stabilized by the delocalization of the nitrogen lone pair into an S-X 1* bond (the anomeric effect).48 All the S–N distances are equal within experimental error [|d(S–N)| = 1.60 (8.12a),49 1.59 Å (8.12b)50].

The cyclic trimer 8.12a is an important reagent in S–N chemistry as a source of both cyclic and acyclic S-N compounds (Scheme 8.3).37 In part, this synthetic utility stems from the ease with which 8.12a dissociates into monomeric NSCl in solution. Thus the trimer provides a facile source of the [SN]+ cation (Section 5.3.1). Monomeric NSCl, generated from (NSCl)3 undergoes a [2 + 4] cycloaddition reaction with hexafluorobutadiene to give a six-membered ring (cf. Scheme 8.1), but it reacts as a nitrene with fluorinated alkenes to give N- (chlorosulfenyl)aziridines (Eq. 8.15).51

The reactions of (NSCl)3 with sodium alkoxides to give (NSOR)352 and with AgF2 to produce 8.12b46 are two examples of transformations that occur with retention of the six-membered ring. The S3N3 ring in 8.12b is more robust than that in 8.12a. For example, the salts