Thiazyl

Polymer and chain formation is another property of chalcogen-nitrogen compounds that distinguishes them from their oxygen analogues. In addition to the unique, superconducting poly(sulfur nitride) (SN) (1.24) (Section 14.2), a variety of poly(thiazyl) chains such as RS5N4R (1.25) (Section 14.3) have been characterized. Interest in these chains stems from their possible use as models for the behaviour of (SN) and as components in molecular materials, e.g., as molecular wires. 

A. W. Cordes, R. C. Haddon and R. T. Oakley, Heterocyclic Thiazyl and Selenazyl Radicals Synthesis and Applications in Solid-State Ai chitecture, in R. Steudel (ed.) The Chemistry of Inorganic Heterocycles, Elsevier, pp. 295-322 (1992). 

J. M. Rawson and F. Palacio, Magnetic Properties of Thiazyl Radicals, Structure and Bonding, 100, 93 (2001). 

Thiazyl salts were first prepared in 1971 by the reaction of NSF with AsFs or SbFs. They may also be obtained from (NSC1)3 by reaction with (a) AgiAsFe] in liquid SO2 (Eq. 5.9) or (b) AICI3 in CH2CI2 under the influence of heat or ultrasound. ... 

The sulfur-nitrogen bond length in thiazyl salts is about 1.42 A and the vibrational frequency [v(SN] occurs at 1437 cm in [SNJiAsFg]. The [SN]" cation exhibits an " N NMR resonance at ca. 200 ppm and this technique is useful for monitoring reactions of [SN]". ... 

The thiazyl cation is used for the preparation of other important S-N compounds (Scheme 5.3). For example, the insertion reactions with S4N4... 

Monomeric thiazyl halides NSX (X = F, Cl Br) have been characterized in the gas phase, but oligomerization to cyclic species, e.g., (NSX)3 (X = F, Cl) and (NSF)4, occurs in the condensed phase (Section 8.7). These ligands can be stabilized, however, by coordination to a transition metal. The NSF complexes are conveniently prepared in SO2 (Eq. 1.6) The monomeric fluoride NSF is conveniently generated in situ by thermal decomposition of FC(0)NSF2 or Hg(NSp2)2 (Section 8.2). 

Thiazyl trifluoride NSF3 is more thermally stable and easier to handle than NSF (Section 8.3). It can be introduced into transition-metal complexes by SO2 displacement reactions (Eq. 7.8). An alternative route to metal-NSF3 complexes is shown in Eq. 7.9. 

The reagent NSF3 may also react via oxidative addition of an S-F bond to a metal centre to give a complex of the thiazyl difluoride anion [NSF2] , which is readily hydrolyzed to an NSO complex (Scheme 7.3). ... 

Thiazyl fluoride is a moisture-sensitive, thermally unstable gas. It is conveniently generated by decomposition of compounds which already... 

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 n-system of the N=S bond (b) reactions at the nitrogen centre (c) nucleophilic substitution reactions (d) halide abstraction, and (e) halide addition. Examples of each type of behaviour are illustrated below. 

Thiazyl trifluoride, a colourless gas with a pungent odour, is prepared by the oxidative decomposition of FC(0)NSF2 with Agp2 (Eq. 8.5).NSF3 is kinetically very stable even in the liquid form. The chemical inertness of NSF3 resembles that of SFe. For example, it does not react with sodium metal below 200°C. ... 

A different type of behaviour is observed with the chloro Lewis acid BCI3. With this reagent halogen exchange occurs to produce the acyclic cation [N(SC1)2] , as the [BCU] salt, rather than NSCf. " Thiazyl trichloride NSCI3 is predicted to be unstable with respect to NSCl -1-Cl2. ... 

Another possible modification of poly(sulfur nitride) that is expected to produce conducting polymers is the replacement of alternating sulfur in the thiazyl chain by an RC unit, i.e., [(R)CNSN]x. This type of polymer would have five r-electrons per four atoms in the repeating unit and, consequently, would have a partially occupied conducting band. The prospect of tuning the electronic properties of this polymer by... 

The simplest chain compounds of the type RS NyR are the sulfur diimides RNSNR (Section 10.4) The other known thiazyl chains are summarized in Table 14.1. They can be conveniently classified as sulfur-rich, nitrogen-rich or even-chain species. 

The incorporation of S-N chains between metal centres by the use of heteroaryl substituents in complexes of the type 14.7 has been proposed as a way to generate new materials that may function as molecular wires. However, the synthesis of thiazyl chains bearing metal-binding sites has yet to be achieved. 

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