Synthesis of fluorous sulfur/carbon/sulfur pincer ligands and palladium complexes: New catalyst precursors for the Heck reaction

Dinuclear platinum(II) sulfide–thiolate complexes [Pt2(μ-S)(μ-SR)(PPh3)4]+ containing fluorinated substituents and the identification of a S⋯C6F5 π interaction in the crystal structure of [Pt2(μ-S)(μ-SCH2C6F5)(PPh3)4]BPh4·2C6H6

“…This chemical shift is similar to that observed for the SCH 2 protons in the butylthiolate analogue [Pt 2 (l-S)(l-S n Bu) (PPh 3 ) 4 ] + (2.29 ppm), but somewhat more shielded than the SCH 2 protons in the (longer chain) free thiol HSCH 2 CH 2 (CF 2 ) 10 CF 3 (2.70-2.90 ppm) [21] and the related sulfide S(CH 2 CH 2 (CF 2 ) 7 CF 3 ) 2 (2.79 ppm) [22]. The CH 2 CF 2 protons of 2 appear as a complex multiplet around d 1.3 ppm, somewhat shielded from 2.30 to 2.55 ppm observed in HSCH 2 CH 2 (CF 2 ) 10 CF 3 , and 2.34-2.47 ppm in S(CH 2 CH 2 (CF 2 ) 7 CF 3 ) 2 .…”

Synthesis, characterization, photophysical properties, and catalytic activity of an SCS bis(N-heterocyclic thione) (SCS-NHT) Pd pincer complex

“…13 Sulfur-containing pincer ligands have been shown to exhibit a great deal of architectural diversity and variations in their design including lateral donors such as thioethers, 14-21 thioamides [22][23][24][25][26][27][28] or phosphine sulfides. [17][18][19]34,35 Additionally, thione and bisthione ligands have been successfully applied in catalysis. [17][18][19]34,35 Additionally, thione and bisthione ligands have been successfully applied in catalysis.…”

Fluorous Organometallic Chemistry

“…The palladium(II) complex performed reasonably as a catalyst for the Heck reaction under standard conditions and was recycled four times using a fluorous solid-phase extraction protocol. Analogous alkyl-and aryl-SCS pre-ligands (XVI and XVII) have also been reported [128,129]. Coordination of the pre-ligands to palladium(II) is straightforward affording complexes with two fluorous ponytails, and the aryl-SCS-PdCl complex (25) has been structurally characterised.…”