Room-Temperature Carbon–Sulfur Bond Activation by a Reactive (dippe)Pd Fragment

Abstract

Supporting Information Table of Contents ________________________________________________________________________________________Experimental details for the structure determination of 9. S-72Experimental details for the structure determination of 10. S-93Experimental details for the structure determination of 14. S-106Experimental details for the structure determination of 14 and 15. S-126Experimental details for the structure determination of (dippe)Pd(Cl) 2 . S-143

C–S Bond Activation

“…Recently, Jones reported that dippe-ligated palladium complex can cleave the C-S bond of diphenyl sulfide even at room temperature [12,21]. They prepared an equivalent of 14-electron Pd(dippe) by reducing PdCl2(dippe) with NaHBEt3.…”

“…disproportionation into nickelathiacycle 12, dinuclear Ni(I) μ-sulfide complex 13, and dibenzothiophene in a ratio of 1:1:2. Later, platinum [11] and palladium [12] analogues of 11 having the strongly electron-donating dippe ligand were also isolated.…”

Mechanistic Insights in the Exchange of Arylthiolate Groups in Aryl(arylthiolato)palladium Complexes Supported by a Dippe Ligand

“…We have recently reported rapid C–S activation of thiophenes by a mixture of [Pd­(dippe)­(μ-H)] 2 ( 1a ) and dinuclear Pd(0), [(μ-dippe)­Pd] 2 ( 1b ) (dippe = 1,2-bis­(diisopropylphosphino)­ethane), to generate palladium­(II) C–S activated products . The mixture of complexes 1a and 1b furnishes the highly reactive 14-electron (dippe)Pd fragment, which is responsible for the activation of the carbon–sulfur bonds in thiophenes and thioethers.…”

Carbon–sulfur bond cleavage of benzothiophene by Cp∗Co(C2H4)2

“…Our group has also investigated the activation of thiophene using precursors for the reactive [12,13], Pd [14,15], and Pt [14]. The [Pt(dippe)] fragment showed unique reactivity in that it was observed to insert into the hindered C-S bond of 4,6-dimethyldibenzothiophene (eq 1) [16].…”