Abstract
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.
Highlights
Phosphines are one of the most important and widely used ligands in homogeneous catalysis and organometallic chemistry due to the extensive options to modify their electronic and steric properties by varying their substitution pattern [1,2,3,4]
Triarylphosphines bearing fluorine atoms or fluorinated substituents are characterized by a higher steric demand and a lower basicity than the non-halogenated counterparts which might lead to changes in the reactivity [5]
Arylphosphines containing a CF3 group have been studied for catalytic processes such as hydroformylation [14], C-C coupling [13,15,16,17] as well as hydroalkylation reactions [18]
Summary
Phosphines are one of the most important and widely used ligands in homogeneous catalysis and organometallic chemistry due to the extensive options to modify their electronic and steric properties by varying their substitution pattern [1,2,3,4]. Arylphosphines containing a CF3 group have been studied for catalytic processes such as hydroformylation [14], C-C coupling [13,15,16,17] as well as hydroalkylation reactions [18]. They present an alternative to fluoroarylphosphines with respect to the increased electron-withdrawing properties of the phosphine
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