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Fischer, Malte; Jaugstetter, Maximilian; Schaper, Raoul; Schmidtmann, Marc; Beckhaus, Rüdiger

Cationic Group 4 Complexes (M = Ti, Zr, Hf): Modifications and Limitations in the Design of Tridentate Cp,O,P‐Ligand Frameworks Built Directly in the Coordination Sphere of the Metal

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  • Medientyp: E-Artikel
  • Titel: Cationic Group 4 Complexes (M = Ti, Zr, Hf): Modifications and Limitations in the Design of Tridentate Cp,O,P‐Ligand Frameworks Built Directly in the Coordination Sphere of the Metal
  • Beteiligte: Fischer, Malte; Jaugstetter, Maximilian; Schaper, Raoul; Schmidtmann, Marc; Beckhaus, Rüdiger
  • Erschienen: Wiley, 2018
  • Erschienen in: European Journal of Inorganic Chemistry
  • Sprache: Englisch
  • DOI: 10.1002/ejic.201801016
  • ISSN: 1434-1948; 1099-0682
  • Schlagwörter: Inorganic Chemistry
  • Entstehung:
  • Anmerkungen:
  • Beschreibung: <jats:p>The reactions of monopentafulvene complexes <jats:bold>Ti1</jats:bold>, <jats:bold>Zr1</jats:bold>, and <jats:bold>Hf1</jats:bold> with bidentate <jats:italic>O</jats:italic>,<jats:italic>P</jats:italic>‐ligand precursors <jats:bold>L1</jats:bold>–<jats:bold>L3</jats:bold> to form the corresponding cationic complexes employing an established three‐step synthetic protocol [insertion, methylation, activation with B(C<jats:sub>6</jats:sub>F<jats:sub>5</jats:sub>)<jats:sub>3</jats:sub>] are investigated. Ligands <jats:bold>L1</jats:bold>–<jats:bold>L3</jats:bold> are designed to have different sized spacers between the carbonyl and diphenylphosphine functional groups. The attempts to react <jats:bold>Ti1</jats:bold>, <jats:bold>Zr1</jats:bold>, and <jats:bold>Hf1</jats:bold> with acetyldiphenylphosphine (<jats:bold>L1</jats:bold>) proved to yield undesired products at various steps in the synthetic sequence. When <jats:bold>Ti1</jats:bold> is used, <jats:bold>Ti2</jats:bold> is formed and diphenylphosphine is released at the same time. Compound <jats:bold>Ti2</jats:bold>, with the exocyclic double bond, is the formal product of insertion of the smallest ketene (H<jats:sub>2</jats:sub>C=C=O) into the Ti–C<jats:sub>exo</jats:sub> bond. Starting with <jats:bold>Zr1</jats:bold> results in isolation of the insertion product <jats:bold>Zr2</jats:bold> without loss of diphenylphosphine, but a byproduct is formed during the reaction with <jats:bold>L1</jats:bold>. Subsequent methylation with methyllithium yields a complex reaction mixture. <jats:bold>Hf1</jats:bold> reacts cleanly with <jats:bold>L1</jats:bold> to the insertion product <jats:bold>Hf2</jats:bold>. Also, the methylation reaction selectively yields <jats:bold>Hf3</jats:bold> as the result of chloride/methyl exchange, but final activation with B(C<jats:sub>6</jats:sub>F<jats:sub>5</jats:sub>)<jats:sub>3</jats:sub> causes decomposition and release of diphenylphosphine. The use of the ligand precursors <jats:bold>L2</jats:bold> and <jats:bold>L3</jats:bold> with two methylene groups or an aryl group as linkers between the functional groups selectively provides the desired cationic complexes <jats:bold>Ti6</jats:bold>, <jats:bold>Zr6</jats:bold>, <jats:bold>Hf6</jats:bold>, and <jats:bold>Ti9</jats:bold> in good to excellent overall yields.</jats:p>