Synthesis, Structures, Ligand Substitution Reactions, and Electrochemistry of the Nitrile Complexes cis-[Ru(dppm) 2 Cl(NCR)] + PF 6 – (dppm = Bis(diphenylphosphino)methane, R = CH3 , C2H5, t Bu, Ph)
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چکیده
Isomerically pure nitrile complexes eis [Ru(dppm)zCI(NCRW (2a-d) are formed upon chloride displacement from eis-[Ru(dppm)ZChJ (1) or, alternatively, by ligand substitution from the acetonitrile complex 2a. This latter approach does also allow for the introduction of pyri dine (3 a,b), heptamethyldisilazane (4) or isonitrile ligands (5). All complexes are obtained as the configurationally stable eis-isomers. Only eis-[Ru(dppmhCI(CN'BuW slowly isomerizes to the trans from. The solid state structures of the CH3CN, C2HsCN and the trans-'BuNC complexes were established by X-ray crystallography. Electrochernical investi gations of the nitrile complexes 2 a-d show in addition to a chemically reversible one-electron oxidation an irrversible reduction step. In CH2Clz solution, eisand tran.\' [Ru(dppmhCI2J have been identified as the final products of the electrochemically induced reaction sequence. Synthese, Strukturen, Ligandenaustauschreaktionen und Elektrochemisches Verhalten der NitriIkomplexe cis-[Ru(dppmhCI(NCR)t PF6(dppm = Bis( diphenylphosphino )methan, R = CH3, C2Hs, IBu, Ph) InhaItsiibersicht. Isomerenreine Nitrilkomplexe eis [Ru(dppm)zCI(NCRW (2a-d) sind, ausgehend von eis [Ru(dppmhCI2J (1), durch Chloridaustausch od er durch Substitution des Acetonitrilliganden von 2 a in einfacher Weise zuganglich. Die zweite Methode erlaubt auch die Ein ftihrung von Pyridin(3 a,b), Amin(4) oder Isonitrilligan den (5), wobei die Substitutionsprodukte als konfigurations stabile eis-Isomere erhalten werden. Lediglich im Falle von eis-[Ru(dppmhCI(CN'BuW tritt Isomerisierung zur trans-
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تاریخ انتشار 2011