Anion Metathesis in Facile Preparation of Olefin Metathesis Catalysts Bearing a Quaternary Ammonium Chloride Tag

◊ J.P. and M.P. contributed equally to this work

Dedicated to Professor Mieczysław Mąkosza on the occasion of his 85^th birthdayó

Published as part of the Cluster Metathesis beyond Olefins

Abstract

Easy and efficient method for preparation of all-chloro ruthenium catalysts bearing a quaternary ammonium tag was developed. The key anion metathesis reaction was made with AgCl, and the facile recycling of silver wastes was demonstrated. The developed method transforms more accessible, yet poorly characterised mixed chloro/iodo Ru complexes into valuable all-chloro catalysts, useful in aqueous metathesis. Practical utility of the developed anion metathesis reaction was demonstrated by preparation of a commercial Ru catalyst, StickyCat™, on a 5 gram scale.

Key words

metathesis - tagged catalysts - ion exchange - silver chloride - polar solvents

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• 22 Typical ProcedureA 4 mL oven-dried vial was charged with chloride salt (30 equiv for AgCl, CuCl and NaCl, 15 equiv. for PbCl₂ and CuCl₂). The vial was evacuated, three times flushed with argon, solution of Ru10 in dry CD₂Cl₂ (1 mL, concentration 64 mg/mL) was added, and the resulting mixture was stirred for 30 min (600 rpm) at room temperature. The mixture was centrifuged (3 min, 4000 rpm), and the solution was examined by ¹H NMR spectroscopy and TLC (alumina plates). Crude product was purified by column chromatography (neutral alumina, 10% DCM/MeOH).
• 23 https://www.apeiron-synthesis.com/katalizatory/fixcat/ (accessed Feb 13, 2019).
• 24 Large-Scale ExperimentIn 100 mL oven-dried round-bottom flask AgCl (0.95 g, 0.66 mmol, 1.1 equiv. per iodide) and Ru10 (containing 91% of [Ru](Cl)₂ and 9% of [Ru](Cl)I complexes, NR₄ ⁺Cl^–: NR₄ ⁺I^– = 20:80, 5 g, 0.6 mmol, 1 equiv.) were suspended in CH₂Cl₂ (80 mL), and the resulting mixture was stirred for 30 min (300 rpm) at room temperature. The mixture was centrifuged (4000 rpm), filtered through Büchner funnel with Teflon filter (pore size 0.2 μm) and flushed with MeOH. Filtrate was filtered through short pad of neutral Celite^® (5 g), solvent was evaporated, crude product was dissolved in minimal amount of CH₂Cl₂, and precipitated with heptane. Precipitate was washed with diethyl ether and dried overnight under vacuum to afford Ru4 as a light green powder (4.16 g, 95%).
• 25 Silver RecyclingIn a 50 mL beaker the mixture of silver halides (1 g) was dissolved in H₂SO₄ (1 mL). H₂O₂ (50% aqueous solution) was slowly added until evacuation of iodine was finished (approx. 1.2 mL). The mixture was stirred for 1 h at 110 °C, cooled to room temperature, diluted with H₂O (20 mL), and treated with concentrated HCl to precipitate crude AgCl. Colourless precipitate was filtered, washed with water, and solubilised in ammonia. Water (20 mL) was added followed by concentrated HCl to precipitate AgCl which was filtered, washed with water, acetone, diethyl ether, and dried overnight under high vacuum at 80 °C to provide pure product with 83% yield ( 858 mg).
• 26 We are grateful to the referee for this suggestion.