The Synthesis and Characterization of Stable Radicals Containing the Thiazyl (SN) Fragment and Their Use as Building Blocks for Advanced Functional Materials - Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds - page 323

Figure 9.4 Schematic of the structure of (SN) x . Dashed lines indicate interchain S-S contact; see text for
details. 45

9.3 “Organothiazyl” radicals

Many different classes of thiazyl radicals exist in which “SN” units are combined with carbon - often
(but not always) in cyclic structures - and, as such, lie at the interface of organic and inorganic chemistry.
These “organothiazyl” radicals generally do not suffer from the shock sensitivity which plagues many binary
sulfur - nitrogen compounds, and the synthetic routes tend to be less mechanistically complex. Moreover,
the organic components of many of these radicals - either carbon as a con stituent of a

conjugated radical
or as a sub stituent on nitrogen, sulfur or carbon - open up the possibility of making several derivatives of
a particular radical class, and therefore of controlling the chemical and physical properties of these radical
classes.

π

9.3.1 Thioaminyl radicals
Thioaminyl radicals [RNSR ] • 5 are the simplest thiazyl-based “organic” radicals. First made in the 1970s,
these radicals have been studied predominantly by Miura. Thioaminyls are normally made by oxidation of
sulfenamides 6 , which are in turn made from the condensation of amines (RNH 2 ) and sulfenyl chlorides
(ClSR ) (Scheme 9.2). The radicals can also be made by photolysis of dimercaptoamines 8 RN(SR ) 2 . 47

N

B:

R'

RNH 2 + ClSR'

R S

− BH + Cl −

6

PbO 2

R'

S R

S

R' N

h n

N R'

N R'

R S

N R'

R S

R S

5

8

7

Scheme 9.2