A SF5 Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes

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.

Chemistry of Pentafluorosulfanyl Derivatives and Related Analogs: From Synthesis to Applications

“…Their X-ray data showed that SF 5 -triphenylphosphines have a larger Tolman cone angle compared to para-substituted phosphine ligands bearing N-(CH 3 ) 2 , CH 3 , OCH 3 , F, and CF 3 substituents. [112] Finally, the SF 5 group has been used as an electron acceptor in organic fluorophores. The group of Chan reported a series of push-pull dyes 156 a-d featuring an amine donor and SF 5 acceptor group.…”

“…The SF 5 moiety was incorporated as well in phosphine‐based ligands by Braun and co‐workers. Their X‐ray data showed that SF 5 ‐triphenylphosphines have a larger Tolman cone angle compared to para ‐substituted phosphine ligands bearing N(CH 3 ) 2 , CH 3 , OCH 3 , F, and CF 3 substituents [112] …”

Celebrating Todd Marder: 65th Birthday and His Contributions to Inorganic Chemistry

“…Professor Todd B. Marder has contributed significantly to expand the scope of boron chemistry, and it is an honor to celebrate his achievements, and mark his 65th birthday with a Special Issue of Molecules : “Boron in Catalysis and Materials Chemistry: A Themed Issue in Honor of Professor Todd B. Marder on the Occasion of His 65th Birthday”. It includes excellent review articles on conjugated N^C-organoboron materials, and tri(boryl)-alkanes and -alkenes as versatile reagents in organic synthesis [ 31 , 32 ], and research articles depicting diversity [ 33 , 34 , 35 , 36 , 37 , 38 , 39 ], as noted in the research interests of Professor Marder. We thank all the authors for joining us to congratulate Todd, and for making this issue a successful one through their excellent scientific contributions.…”