Synthesis of Highly Fluorinated Arene Complexes of [Rh(Chelating Phosphine)]⁺ Cations, and their use in Synthesis and Catalysis

Abstract

The synthesis of rhodium complexes with weakly binding highly fluorinated benzene ligands is described: 1,2,3‐F3C6H3, 1,2,3,4‐F4C6H2 and 1,2,3,4,5‐F5C6H are shown to bind with cationic [Rh(Cy2P(CH2)xPCy2)]+ fragments (x=1, 2). Their structures and reactivity with alkenes, and use in catalysis for promoting the Tishchenko reaction of a simple aldehyde, are demonstrated. Key to the synthesis of these complexes is the highly concentrated reaction conditions and use of the [Al{OC(CF3)3}4]− anion.

From ferrocene to 1,2,3,4,5-pentafluoroferrocene: halogen effect on the properties of metallocene

“…[16][17][18] Despite these interests and the role of metallocenes in many of these areas of fundamental and applied interest, few polyfluorometallocenes have been described, and structureproperty relationships are limited in scope. [19][20][21] Concerning η 6 coordination compounds, a few arene-vanadium, 22 chromium [23][24][25][26][27][28] and -rhodium 29,30 complexes with up to six fluorine atoms on the aromatic ring have been reported. However, η 5 -coordination complexes are limited to a handful of examples (Figure 1).…”

Front Cover: Ortho‐F,F‐DPEphos: Synthesis and Coordination Chemistry in Rhodium and Gold Complexes, and Comparison with DPEphos (Eur. J. Inorg. Chem. 24/2022)

“…[52,53] 4 ], [28] [Rh(o-H,H-DPEphos)(acetone) 2 ][BAr F 4 ], [24,25] 4 ], whereas with ortho-i Pr a CÀH activated product results. [17] Here, we contrast the activation products of 3-H,H and 3-F,F after treatment with H 2 in the less coordinating [54,55] solvent, 1,2-F 2 C 6 H 4 (Scheme 4). An atmosphere of 1 bar H 2 was applied to a 1,2-F 2 C 6 H 4 solution of 3-H,H and a color change from orange to dark red was observed after several minutes.…”

Ortho‐F,F‐DPEphos: Synthesis and Coordination Chemistry in Rhodium and Gold Complexes, and Comparison with DPEphos

“…[52,53] 4 ], [28] [Rh(o-H,H-DPEphos)(acetone) 2 ][BAr F 4 ], [24,25] 4 ], whereas with ortho-i Pr a CÀ H activated product results. [17] Here, we contrast the activation products of 3-H,H and 3-F,F after treatment with H 2 in the less coordinating [54,55] solvent, 1,2-F 2 C 6 H 4 (Scheme 4). An atmosphere of 1 bar H 2 was applied to a 1,2-F 2 C 6 H 4 solution of 3-H,H and a color change from orange to dark red was observed after several minutes.…”