Fluorinated building blocks by C-F bond cleavage: Catalytic C-F activation reactions that give novel dioxaborolanes have been developed (see scheme). The reactions proceed at room temperature, and catalytic intermediates are presumably rhodium hydride and boryl species.
Fluorierte Bausteine durch C‐F‐Bindungsspaltung: Die Synthese neuartiger Dioxaborolane durch katalytische C‐F‐Aktivierung wird vorgestellt (siehe Schema). Die Reaktionen verlaufen bei Raumtemperatur, wobei als katalytische Zwischenstufen vermutlich Rhodiumhydrid‐ und Borylspezies auftreten.
The synthesis of the triarylphosphine, P(p-C6H4SF5)3 containing a SF5 group, has been achieved. The experimental and theoretical studies showed that P(p-C6H4SF5)3 is a weaker σ-donor when compared with other substituted triarylphosphines, which is consistent with the electron-withdrawing effect of the SF5 moiety. The studies also revealed a moderate air stability of the phosphine. The σ-donor capabilities of P(p-C6H4SF5)3 were estimated from the phosphorus-selenium coupling constant in SeP(p-C6H4SF5)3 and by DFT calculations. The behavior of P(p-C6H4SF5)3 as ligand has been investigated by the synthesis of the iridium and rhodium complexes [MCl(COD){P(p-C6H4SF5)3}], [MCl(CO)2{P(p-C6H4SF5)3}2] (M = Ir, Rh), or [Rh(µ-Cl)(COE){P(p-C6H4SF5)3}]2, and the molecular structures of [IrCl(COD){P(p-C6H4SF5)3}] and [Rh(µ-Cl)(COE){P(p-C6H4SF5)3}]2 were determined by single X-ray diffraction. The structures revealed a slightly larger cone angle for P(p-C6H4SF5)3 when compared to other para-substituted triarylphosphines.
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