Elimination sulfido

There are no reports on electrophilic attack at ring carbon or nitrogen. Regarding ring sulfur atom, it has been reported that oxathiazolones (49), act as sulfur sources in their reaction with Mn(CO)s yielding a sulfido cluster of the type [Mn3(CO)9(/i3-S)2] by elimination of PhCN and CO2 <930M1009>. 

The deprotonation reaction of Cp2Ti(SH)2 with NaH in THF proceeds unexpectedly with the elimination of GpH to give the anionic sulfide-bridged titanium(iv) dimer, Na2[CpTi(/x-S)(S)]2. The molecular structure of this compound has been determined by X-ray diffraction and shows a terminal sulfido ligand with a short Ti-S bond distance of ca. 2.2 A, indicating nearly double bond character (Scheme 417). It adopts a yy/z-Ti=S configuration and is stabilized by interactions with THF-solvated sodium cations.1009... 

In some cases the oxidative addition reaction has been observed to proceed further with the elimination of dihydrogen and the consequent formation of a stable sulfido complex, in a way the reverse reaction of the activation of hydrogen by Cp 2Ti=S described in the preceding section. For instance, the Zr(n) complex Cp 2Zr(CO)2 reacts with excess HjS in the presence of pyridine to yield the corresponding bis(hydrosulfido) derivative Cp Zr(SH),. This reaction takes place via an initial oxidative addition of HjS to yield Cp Zr(H)(SH) followed by hydrogen elimination in the presence of pyridine to form a terminal sulfido complex Cp Zr(S)(py) the latter undergoes a second oxidative addition of H2S to finally produce the bis(hydrosulfido) complex, as shown in Eq. 5.14 [2]. 

D. Rabinovich and G. Parkin,/. Am. Chem. Soc., 113, 5904 (1991). The Syntheses, Structures and Reactivity of Monomeric Tungsten(IV) and Tungsten(Vl) Bis(Sulfido) Complexes Facile Elimination of H2 from H2S. G. Parkin, personal communication, 1994. 

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