To Coordinate or not to Coordinate: The Special Role of Chalcogen Ether Functionalities in the Design of Twofold Functionalized Cyclopentadienyl Ligands [Cp, O, Ch (Ch = S, Se)]. Issue 6 (8th March 2019)

• Record Type: Journal Article
• Authors: Fischer, Malte; Schmidtmann, Marc; Beckhaus, Ruediger
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 645:Issue 6/7(2019)
• Page Start: 595
• Page End: 604
• Publication Date: 2019-03-08
• Subjects: Pentafulvene -- Titanium -- Cationic complex -- Ligand design -- NMR spectroscopy; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201900012
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract : The solvent‐ and catalyst free synthesis of two β‐thio ketonesL1a andL1b is reported.L1a, L1b, and a β‐seleno ketoneL1c were successfully employed as ligand precursors in the synthesis of a novel series of cationic titanium complexes4a –4c via a well‐established reaction sequence: insertion of the carbonyl functional group into the polarized Ti–Cq, exo bond of the monopentafulvene complex Cp*Ti(Cl)(π‐η 5 :σ–η 1 ‐C5 H4 =C R 2 ) (1 ) (C R 2 = adamantylidene), subsequent methylation, and final activation with B(C6 F5 )3 . The cationic titanium complexes4a –4c bear twofold functionalized cyclopentadienyl [Cp, O, Ch ( Ch = S, Se)] ligand frameworks built directly in the coordination sphere of the metal, in which the chalcogen ether functionalities do not coordinate to the central metal atoms as demonstrated by NMR experiments. Consequently, Cp, O σ, π chelating ligand systems are formed with free coordination sites at the central titanium atoms and pendant chalcogen ether moieties. Abstract :