Oligomerization Chemistry of a Metallabenzene Cycloadduct. Synthesis and Structure of an Organometallic Crown Compound1

Author:

Bleeke John R.1,Behm Robert1,Beatty Alicia M.1

Affiliation:

1. Department of Chemistry, Washington University, St. Louis, Missouri 63130

Publisher

American Chemical Society (ACS)

Subject

Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry

Reference7 articles.

1. Synthesis, Structure, Spectroscopy, and Reactivity of a Metallabenzene1

2. Metallabenzene chemistry

3. Synthesis of compound3. Compound2(0.26 g, 3.7 × 10-4mol) was dissolved in ∼30 mL of tetrahydrofuran and stirred at 25 °C for 6 h (to establish equilibrium between2and3). The volatiles (including PEt3) were then removed under vacuum. The resulting yellow residue was redissolved in tetrahydrofuran, stirred for an additional 6 h, and again stripped to dryness. This procedure was repeated five times, leading to a yellow powder that contained3in >90% purity. The powder was dissolved in acetone and cooled to −30 °C overnight, producing crystals of3. Yield:  76%. Anal. Calcd for C46H93Ir2P5S4:  C, 42.05; H, 7.15. Found:  C, 42.35; H, 7.50.

4. Synthesis of compound4. Compound2(0.34 g, 4.7 × 10-4mol) was dissolved in ∼30 mL of toluene and heated at reflux for 1.5 h, while purging with a slow stream of N2to remove PEt3. The toluene was then removed under vacuum, and the yellow residue was dissolved in pentane and filtered through Celite. The pentane was removed under vacuum, and the resulting yellow powder was dissolved in acetone. Slow evaporation of the acetone solution yielded crystalline4. Yield:  97%. Anal. Calcd for C60H117Ir3P6S6:  C, 40.18; H, 6.59. Found:  C, 40.16; H, 6.73.

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1. Metallaaromatic Chemistry: History and Development;Chemical Reviews;2020-10-19

2. Recent Advances in Metallaaromatic Chemistry;Chemistry - A European Journal;2017-12-13

3. Theoretical Studies of Metallabenzenes: From Bonding Situation to Reactivity;Metallabenzenes;2017-07-29

4. Aromaticity of metallabenzenes and related compounds;Chemical Society Reviews;2015

5. Metallabenzenes and Metallabenzenoids;Advances in Organometallic Chemistry Volume 60;2012

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