Synthesis, Structure and Reactivity of Trimethylsilyl-Substituted Phosphametallocenes

• Published in: European Journal of Inorganic Chemistry Vol. 2007; no. 4; pp. 553 - 561
• Main Authors: Loschen, Rebekka, Loschen, Christoph, Frank, Walter, Ganter, Christian
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.02.2007; WILEY‐VCH Verlag; Wiley
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Conformation analysis; Metallocenes; P ligands; Phosphaferrocenes; Physical Sciences; Science & Technology; Silicon; conformation analysis; AUXILIARY BASIS-SETS; STERICALLY DEMANDING LIGANDS; PLANAR CHIRALITY; TRIPLE-DECKER COMPLEXES; HALF-SANDWICH COMPLEXES; phosphaferrocenes; metallocenes; silicon; APPROXIMATE COULOMB POTENTIALS; P ligands; ELECTROPHILIC SUBSTITUTION; DYNAMIC SOLUTION BEHAVIOR; GAUSSIAN-BASIS SETS; ORGANOSILICON COMPOUNDS
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.200600914

New sterically crowded phosphaferrocene and ‐ruthenocene derivatives were synthesized via the 2,5‐bis(trimethylsilyl)phospholide anion 5. Their reactivity with regard to the exchange of the Me3Si groups for other functional groups was examined. X‐ray structures were determined for the mono‐ (6) and the 1,1′‐diphosphaferrocene (8). The activation barrier for ring–ring rotation in 8 was determined by NMR spectroscopy and supported by DFT calculations. Attempts to prepare 2,5‐difunctional phosphaferrocenes through electrophilic substitutions were unsuccessful, but yielded en route a new bidentate P,P ligand (3) and its Mo(CO)4 complex, which were both characterized by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)