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Hexakis(PCP-Platinum and -Ruthenium) Complexes by the Transcyclometalation Reaction and Their Use in Catalysis

✍ Scribed by Harm P. Dijkstra; Martin Albrecht; Serenella Medici; Gerard P. M. van Klink; Gerard van Koten

Book ID
101391882
Publisher
John Wiley and Sons
Year
2002
Tongue
English
Weight
103 KB
Volume
344
Category
Article
ISSN
1615-4150

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✦ Synopsis

Hexakis(PCP-pincer) complexes [C 6 {PtBr-(PCP)} 6 ] (5d) and [C 6 {RuCl(PCP)(PPh 3 )} 6 ] (5e) were synthesized via the transcyclometalation (TCM) procedure. Mixing the hexakis(PCHP-arene) ligand 7 with six equivalents of [PtBr(NCN)] (1a) or [RuCl(NCN)(PPh 3 )] (1b), respectively, resulted in the selective metalation of all PCP-ligand sites and the concomitant formation of six equivalents of the NCHN-arene ligand. This procedure was found to be superior over existing metalation procedures. In addition, hexakisruthenium complex 5e was applied as homogeneous catalyst in the hydrogen transfer reactions of cyclohexanone, acetophenone and benzophenone to the corresponding alcohols. In these reactions, the activity per ruthenium center of 5e was found to be of the same order of magnitude as that of the mononuclear analogue [RuCl(PCP)(PPh 3 )] 3b, indicating that all ruthenium centers act as independent catalytic sites.

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Novel P-Stereogenic PCP Pincer-Aryl Ruth
Novel P-Stereogenic PCP Pincer-Aryl Ruthenium(II) Complexes and Their Use in the Asymmetric Hydrogen Transfer Reaction of Acetophenone
✍ Serenella Medici; Marcella Gagliardo; Scott B. Williams; Preston A. Chase; Seraf 📂 Article 📅 2005 🏛 John Wiley and Sons 🌐 German ⚖ 137 KB 👁 1 views

## Abstract Achiral P‐donor pincer‐aryl ruthenium complexes ([RuCl(PCP)(PPh~3~)]) 4c,d were synthesized __via__ transcyclometalation reactions by mixing equivalent amounts of [1,3‐phenylenebis(methylene)]bis[diisopropylphosphine] (2c) or [1,3‐phenylenebis(methylene)]bis[diphenylphosphine] (2d) and