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) |
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Authors: | Rainer F Winter Thomas Scheiring |
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Abstract: | Isomerically pure nitrile complexes cis‐Ru(dppm)2Cl(NCR)]+ ( 2 a – d ) are formed upon chloride displacement from cis‐Ru(dppm)2Cl2] ( 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)2Cl(CNtBu)]+ slowly isomerizes to the trans from. The solid state structures of the CH3CN, C2H5CN and the trans‐tBuNC complexes were established 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 CH2Cl2 solution, cis‐ and trans‐Ru(dppm)2Cl2] have been identified as the final products of the electrochemically induced reaction sequence. |
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Keywords: | Ruthenium Nitrile complexes Electrochemistry Crystal structure |
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