Ferrocenyl thioethers

Scheme 1.79 Phosphinamidite-thioether ferrocenyl ligands for Pd-catalysed allylic...

Scheme 1.81 Allylic etherifications with phosphinamidite-thioether ferrocenyl ligand.

In addition, Peruzzini et al. developed, in 2007, iridium complexes of planar-chiral ferrocenyl phosphine-thioether ligands that were tested in the hydrogenation of simple alkyl aryl ketones.These complexes were diastereoselec-tively generated in high yields (85-90%) by addition of the corresponding... 

Scheme 8.33 Hydrogenations of alkyl aryl ketones with ferrocenyl phosphine-thioether ligands.

N/S/P-ferrocenyl hgands 61-2 phosphinamidite-thioether ferrocenyl hgands 60-3... 

Table 4.4 Asymmetric hydrogenation of acetophenones using Ir complexes bearing planar chiral ferrocenyl phosphino thioethers. ...

Scheme 5-32 shows a series of ferrocenyl compounds that can be formally considered as derivatives of the ferrocenyl chalcogenols, Fc-EH (E = O, S, Se, Te), including ferrocenyl ethers, thioethers, selenoethers and telluroethers. The analogous l,T-ferrocenediyl compounds, formally derived from fc(EH)2 (E = O, S, Se, Te), are presented in Scheme 5-33 (see Appendix). 

Figure 4.35 The third-generation dendrimers bearing 24 chiral ferrocenyl phosphine-thioether end groups.

A Cr(VI) sulfoxide complex has been postulated after interaction of [CrOjtClj] with MejSO (385), but the complex was uncharacterized as it was excessively unstable. It was observed that hydrolysis of the product led to the formation of dimethyl sulfone. The action of hydrogen peroxide on mesityl ferrocencyl sulfide in basic media yields both mesityl ferrocenyl sulfoxide (21%) and the corresponding sulfone (62%) via a reaction similar to the Smiles rearrangement (165). Catalytic air oxidation of sulfoxides by rhodium and iridium complexes has been observed. Rhodium(III) and iridium(III) chlorides are catalyst percursors for this reaction, but ruthenium(III), osmium(III), and palladium(II) chlorides are not (273). The metal complex and sulfoxide are dissolved in hot propan-2-ol/water (9 1) and the solution purged with air to achieve oxidation. The metal is recovered as a noncrystalline, but still catalytically active, material after reaction (272). The most active precursor was [IrHClj(S-Me2SO)3], and it was observed that alkyl sulfoxides oxidize more readily than aryl sulfoxides, while thioethers are not oxidized as complex formation occurs. 

The experimental PHIP studies and DFT calculations were also combined to explore the chemistry of Rh(I) complex possessing a chiral ferrocenyl phosphine thioether bidentate ligand [130]. The relative stability of the [Rh(P,S Bu)L2] (L = MeOH, pyridine, or MeCN (P,S Bu) = CpFe[q5-i,2-C5H3(PPh2)(CH2S Bu)]) complexes, their ability to form dihydrides upon interaction with H2, the relative stability of the products, and the mechanisms of the site exchange in the dihydrides were addressed. 

Routaboul L, Vincendeau S, Turrin C-O, Caminade A-M, Majoral J-P, Daran J-C, Manoury E (2007) New phosphorus dendrimers with chiral ferrocenyl phosphine-thioether ligands on the periphery for asymmetric catalysis. J Organomet Chem 692 1064—1073... 

Le Roux E, Malacca R, Manoury E, Poli R, Gonsalvi L, Peruzzini M (2007) Highly efficient asymmetric hydrogenation of alkyl aryl ketones catalyzed by iridium complexes with chiral planar ferrocenyl phosphino-thioether ligands. Adv Synth Catal 349 309-313... 

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