Synthesis and Reactivity of the RuIII Complexes [RuTp(PR3)Cl2] — Precursors for RuTp Dihydrogen Complexes

✍ Scribed by Sonja Pavlik; Michael Puchberger; Kurt Mereiter; Karl Kirchner

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 173 KB
• Volume: 2006
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200600503

✦ Synopsis

Abstract

The air‐sensitive DMF‐containing intermediate [RuTp(PR~3~)(Cl)(DMF)] is formed by refluxing a DMF solution of [RuTp(COD)Cl] (1) in the presence of at least 1 equiv. of PR~3~ (PR~3~ = PPh~3~, PPh~2~__i__Pr, P__i__Pr~3~, and PCy~3~). On exposure to air in the presence of CCl~4~, this complex is readily converted into the respective Ru^III^ complexes [RuTp(PR~3~)Cl~2~] (2a–d). These compounds are air‐stable, readily accessible, permit easy variations as far as the electronic and steric properties of the PR~3~ co‐ligands are concerned, and are reducible to a variety of Ru^II^Tp complexes. Treatment of 2 with NaBH~4~ affords dihydrogen compounds of the type [RuTp(PR~3~)(H)(η^2^‐H~2~)]. Reduction of 2 can also be accomplished with Zn in the presence of CH~3~CN and pyridine, which affords the diamagnetic Ru^II^ compounds [RuTp(PR~3~)(CH~3~CN)~2~]^+^ (4a–c) and [RuTp(PR~3~)(py)Cl] (5). X‐ray structures of representative complexes are presented. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)