Synthesis of (Indenylidene)phosphoranes − A Novel Class of Ligand Precursors for Main-Group and Transition Metal Organometallics

✍ Scribed by Konstantin A. Rufanov; Burkhard Ziemer; Markus Hummert; Stefan Schutte

• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: English
• Weight: 133 KB
• Volume: 2004
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200400664

✦ Synopsis

Bridging ligands / Constrained geometry catalysts / Cyclopentadienyl ligands / Isoelectronic analogues / Isolobal relationship / Phosphoranes / Phosphorus ylides / Indenyl / Sodium IndPPh 2 (1) reacts with RCH 2 Br to form the phosphonium salts [RCH 2 P(Ph) 2 Ind] + Br -(2: R = Ph; 3: R = C 6 F 5 ) in high yields. Oxidation of 1 with H 2 O 2 in THF proceeds smoothly to give the phosphane oxide IndP(O)Ph 2 (4). Dehydrobromination of 2 and 3 with NaH in THF yields the corresponding indenylidenephosphoranes C 9 H 6 =P(Ph) 2 CH 2 R (5: R = Ph; 6: R = C 6 F 5 ). Further deprotonation of 6 with excess NaH results in formation of sodium 1-{[(pentafluorophenyl)methylidene]-