Synthesis and Reactivity of the First η6-Rhodium(I) and η6-Iridium(I) Complexes of 2,6-Bis(trimethylsilyl)phosphinines

✍ Scribed by Marjolaine Doux; Louis Ricard; François Mathey; Pascal Le Floch; Nicolas Mézailles

• Publisher: John Wiley and Sons
• Year: 2003
• Tongue: English
• Weight: 219 KB
• Volume: 2003
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200390095

✦ Synopsis

Abstract

It has been shown that 2 equiv. of 2,3,5,6‐tetraphenylphosphinine (2) react with [Rh(COD)~2~][BF~4~] to yield the bis(η^1^‐phosphinine)Rh^I^ complex 6, whose X‐ray crystal structure is presented. On the other hand, 2,6‐bis(trimethylsilyl)phosphinines 4 and 5 react with Rh^+^ and Ir^+^ precursors to yield the first (η^6^‐phosphinine)Rh^I^ and ‐Ir^I^ complexes 7−10, and 11−12, respectively. The X‐ray crystal structure of complex 8 is presented. Reaction of these η^6^‐phosphinine complexes with water or ethanol yields the first (η^5^‐phosphacyclohexadienyl)Rh^I^ and ‐Ir^I^ complexes 13−17, resulting from the formal 1,1‐addition of RO^−^ and H^+^. DFT calculations comparing isoelectronic (η^6^‐phosphinine)‐ and (η^6^‐benzene)Fe^0^ and ‐Rh^I^ complexes allows the rationalization of the large difference in reactivity of these complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)