Synthesis, Structures, Ligand Substitution Reactions, and Electrochemistry of the Nitrile Complexes cis-[Ru(dppm)2Cl(NCR)]+ PF6– (dppm = Bis(diphenylphosphino)methane, R = CH3, C2H5, tBu, Ph)
✍ Scribed by Rainer F. Winter; Thomas Scheiring
- Publisher
- John Wiley and Sons
- Year
- 2000
- Tongue
- German
- Weight
- 172 KB
- Volume
- 626
- Category
- Article
- ISSN
- 0372-7874
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✦ Synopsis
Isomerically pure nitrile complexes cis-[Ru(dppm) 2 Cl(NCR)] + (2 a±d) are formed upon chloride displacement from cis-[Ru(dppm) 2 Cl 2 ] (1) or, alternatively, by ligand substitution from the acetonitrile complex 2 a. This latter approach does also allow for the introduction of pyridine (3 a,b), heptamethyldisilazane (4) or isonitrile ligands (5). All complexes are obtained as the configurationally stable cis-isomers. Only cis-[Ru(dppm) 2 Cl(CN t Bu)] + slowly isomerizes to the trans from. The solid state structures of the CH 3 CN, C 2 H 5 CN and the trans-t BuNC complexes were es-tablished by X-ray crystallography. Electrochemical investigations of the nitrile complexes 2 a±d show in addition to a chemically reversible one-electron oxidation an irrversible reduction step. In CH 2 Cl 2 solution, cis-and trans-[Ru(dppm) 2 Cl 2 ] have been identified as the final products of the electrochemically induced reaction sequence.