Calcium Complexes Bearing Dianionic or Monoanionic Iminoacenaphthen‐1‐one Ligands: Synthesis, Reactions with Alkynes and Catalysis of L‐lactide Polymerization. Issue 27 (8th August 2022)

• Record Type: Journal Article
• Authors: Lukoyanov, Anton N.; Zvereva, Yulia V.; Parshina, Diana A.; Cherkasov, Anton V.; Ketkov, Sergey Yu.
• Is Part Of: European journal of inorganic chemistry. Volume 2022:Issue 27(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-08
• Subjects: Anions -- Calcium -- Dianions -- N, O-ligands; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202200348
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The reduction of 2‐[(2, 6‐diisopropylphenyl)imino]acenaphthen‐1‐one (dpp‐MIAN) with metallic calcium in THF affords tetrameric [(dpp‐MIAN)Ca(THF)]4 (1 ). A further addition of dpp‐MIAN to complex 1 leads to the formation of paramagnetic species [(dpp‐MIAN)3 Ca]2 Ca (2 ). Both complexes were characterized by X‐ray diffraction. Complex 1 is active towards phenylacetylene and acetylene at temperatures above 80 °C. As a result, cycloaddition products are formed. Their hydrolysis results in a release of the dpp‐MIAN ligand with an attached phenylethynyl or ethynyl moiety to the carbonyl C atom. Complexes 1 and 2 demonstrate catalytic activity in the polymerization of L‐lactide both in solution and in bulk. Abstract : The redox‐active 2‐[(2, 6‐diisopropylphenyl)imino]acenaphthen‐1‐one (dpp‐MIAN) is reduced with calcium metal in THF solution, forming [(dpp‐MIAN) 2− Ca 2+ (THF)]4 (1 ). With an excess of dpp‐MIAN, [(dpp‐MIAN) 1− 3 Ca 2+ ]2 Ca 2+ (2 ) is produced. Complex 1 reacts with acetylene and phenylacetylene giving Ca alkynyl derivatives and catalyzes the polymerization of L‐lactide.