S,N,N'-Substituted sulfurdiimines as ligands

X-ray structure and dynamic behaviour in solution of N-methylthio-N'-2,6-dimethylphenyl).2,6-dimethyl-1,4-quinonediimine formed by the alcoholysis of [Me2 Al{2,6-Me2C6H3NS(Me)NC6H3Me2-2,6}]2

“…It has been shown previously that transition metal complexes containing [ RNS( R')NR]-ligands decompose quantitatively in solution into RN=NR and SR' fragments [ 7,12,14]. It was concluded that for all these metal complexes the formation of RN=NR proceeds intramolecularly via intermediates, which are likely monomeric in nature.…”

“…For RNSNR and RNSO it has been shown that chemical activation and subsequent N=S bond rupture is favoured by initial q2-N=S coo~~ation to low valent electron-rich transition metal atoms ]6,7], The RNS, S and NR fragments so formed may then be captured by formation of cluster complexes [6,7]. Chemical activation and conversion of RNSNR or -RNSO may also take place by addition of organolithium, organomagnesium [11,12] or organoaluminium compounds [5] to the N=S double bond. For the sulfurdiimines this gives the [RNS(R')NR]-ligand which may be transferred to copper(I), silver(I), rhodium(I) or palladium(I1) in metathesis reactions [ 12,131.…”

“…Chemical activation and conversion of RNSNR or -RNSO may also take place by addition of organolithium, organomagnesium [11,12] or organoaluminium compounds [5] to the N=S double bond. For the sulfurdiimines this gives the [RNS(R')NR]-ligand which may be transferred to copper(I), silver(I), rhodium(I) or palladium(I1) in metathesis reactions [ 12,131. The resulting transition metal complexes decompose quantitatively in solution into RN=NR and SR' segments, at a rate which depends on the metal ion and the stereo and electronic properties of R and R' [12,14].…”

“…For the sulfurdiimines this gives the [RNS(R')NR]-ligand which may be transferred to copper(I), silver(I), rhodium(I) or palladium(I1) in metathesis reactions [ 12,131. The resulting transition metal complexes decompose quantitatively in solution into RN=NR and SR' segments, at a rate which depends on the metal ion and the stereo and electronic properties of R and R' [12,14]. The aluminium compounds of this ligand [ 51 also decompose in solution, although in a less specific way.…”

Reactions of sulfurdiimines and sulfinylanilines with [AlMe3]2

“…It has flurther been demonstrated that chemical activation may also take place by addition of LiR' or XMgR' (R' = alkyl, aryl) across one of the N=S double bonds. In the case of sulfurdiimines this affords the uninegative [RNS(R')NR]-ligand [11,12], which may then be bonded to Cu', Ag', Rh' and Pd" via metathesis reactions [12,13]. Table 1 and Table 2 …”