Syntheses and Structures of d¹⁰Coinage Metal Complexes of Electron-Accepting Phosphine Ligands Featuring a 3,3,4,4,5,5-Hexafluorocyclopentene Framework

Abstract

Cu(I), Ag(I), and Au(I) complexes of monophosphine or bisphosphine ligands based on the 3,3,4,4,5,5-hexafluorocyclopentene skeleton were synthesized and structurally characterized by X-ray crystallographic analysis. The electron-withdrawing nature of these polyfluorinated phosphines was experimentally revealed via UV/vis absorption studies and crystal structure analysis. Successful catalytic application of the Au(I) complex for alkyne hydration reactions was investigated.

Diphenyl‐ and Dimesityl‐Phosphanyl‐Substituted 3,3,4,4,5,5‐Hexafluorocyclopentenyl‐Gold(I) Dimers – Syntheses and Solid‐State Structures

“…According to a modified literature procedure, [9] 1,2‐dichloro‐3,3,4,4,5,5‐hexafluorocyclopentene was lithiated with n ‐butyllithium and treated with chlorodiphenylphosphane, or chloro‐/bromodimesitylphosphane [10] to yield 1‐chloro‐2‐diphenylphosphanyl‐3,3,4,4,5,5‐hexafluorocyclopentene ( 1 a ) and 1‐chloro‐2‐dimesitylphosphanyl‐3,3,4,4,5,5‐hexafluorocyclopentene ( 1 b ), respectively (Scheme 2). To synthesize the trimethylstannyl functionalized phosphanes 2 a and 2 b , the precursors 1 a and 1 b were lithiated with sec ‐butyllithium and treated with chlorotrimethylstannane.…”

“…1‐Chloro‐2‐diphenylphosphanyl‐3,3,4,4,5,5‐hexafluorocyclopentene (1 a) . The compound was synthesized by a modified literature procedure: [9] n ‐Butyllithium (9.2 mL, 14.7 mmol, 1.6 m in n ‐hexane) was added dropwise to a solution of 1,2‐dichloro‐3,3,4,4,5,5‐hexafluorocyclopentene (3.00 g, 8.70 mmol) in diethyl ether (30 mL) at −78 °C. The reaction mixture was stirred for further 30 min at the same temperature, chlorodiphenylphosphane (3.24 g, 14.7 mmol) was added dropwise and after complete addition the solution was warmed to ambient temperature over the period of 2 h and stirred for 20 h. The reaction mixture was treated with ammonium chloride (saturated aqueous solution, 30 mL), the aqueous phase was extracted with dichloromethane (3×30 mL) and dried with sodium sulphate.…”

“…Up to this point, only two gold(I) complexes bearing a hexafluorocyclopentene framework, the mononuclear complex F 6 cyp(PPh 2 AuCl)Cl and the semi‐supported complex F 6 cyp(PPh 2 AuCl) 2 , were known. While both complexes exhibit no intermolecular Au⋅⋅⋅Au contacts, the dinuclear compound features intramolecular Au⋅⋅⋅Au contacts (3.014(5) Å) [9] …”

“…While both complexes exhibit no intermolecular Au•••Au contacts, the dinuclear compound features intramolecular Au•••Au contacts (3.014(5) Å). [9]…”