Synthesis, Structure and Reactivity of New Late Transition Metal Complexes Bearing Diphosphane Ligands Derived from Bis(pyrazol-1-yl)methane
✍ Scribed by Antonio Otero; Fernando Carrillo-Hermosilla; Pilar Terreros; Teresa Expósito; Sergio Rojas; Juan Fernández-Baeza; Antonio Antiñolo; Isabel López-Solera
- Publisher
- John Wiley and Sons
- Year
- 2003
- Tongue
- English
- Weight
- 182 KB
- Volume
- 2003
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Abstract
Modification of the multistep synthesis of the previously described bis[5‐(diphenylphosphanyl)pyrazol‐1‐yl)]methane (bppzm, 1) produces the novel diphosphane (diphenylphosphanyl)‐5‐(diphenylphosphanyl)pyrazol‐1‐ylmethane (p4m, 2). Treatment of this ligand with [MCl~2~(PhCN)~2~] (M = Pd, Pt) or [M(COD)(THF)~2~]BF~4~ (M = Rh, Ir) produces [MCl~2~(p4m)] (M = Pd 3, Pt 4) or [M(COD)(p4m)]BF~4~ (M = Rh 5, Ir 6) complexes, which chelate in a P,P‐bidentate fashion. Sulfidation of bppzm and p4m produces the disulfidophosphanes bppzmS~2~ (7) and p4mS~2~ (8). Treatment of 7 and 8 with [PdCl~2~(PhCN)~2~] produces [PdCl~2~(bppzmS~2~)] (9) and [PdCl~2~(pmS~2~)] (10), respectively, in which ligands 7 and 8 act in an N,N‐bidentate chelate fashion. In contrast, ligand 8 reacts with [Rh(COD)(THF)~2~]BF~4~ to produce [Rh(COD)(p4mS~2~)]BF~4~, where ligand 7 acts in a dynamic S,S‐chelate fashion. The activity of some of these complexes in the catalytic hydrogenation of olefins is reported and the single‐crystal X‐ray structures of 4, 8, and 9 have been obtained. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)