Reduktive Dimerisierung von NO an Dirutheniumkomplexen und Bildung eines tridentaten 2, 2‐Bis(diphenylphosphanyl)ethanolato‐Liganden

Abstract

AbstractThe reaction of the trans‐hyponitrito complex [Ru2(CO)4(μ‐η2‐ONNO)(μ‐H)(μ‐PtBu2)(μ‐dppen)] (1, dppen = Ph2PC(=CH2)PPh2) with tetrafluorido boric acid afforded the new complex salt [Ru2(CO)4(μ‐η2‐ONNOH)(μ‐H)(μ‐PtBu2)(μ‐dppen)]BF4 (2) containing the monoprotonate hyponitrous acid as the ligand in the cationic complex. Complex 1 showed a nucleophilic reactivity towards the trimethyloxonium cation resulting in the monoester derivative of the hyponitrous acid [Ru2(CO)4(μ‐η2‐ONNOMe)(μ‐H)(μ‐PtBu2)(μ‐dppen)]BF4 (3). During heating of compound 2 in ethanol under reflux for a short time nitrous oxide was liberated affording unexpectedly a new tridentate 2, 2‐bis(diphenylphosphanyl)ethanolato ligand formed by an intramolecular attack of an intermediate hydroxido ligand towards the unsaturated carbon carbon double bond in the bridging dppen ligand. Thus the complex salt [Ru2(CO)4{μ‐η3‐OCH2CH(PPh2)2}(μ‐H)(μ‐PtBu2)]BF4 (4) was formed in good yields. The new compounds 2, 3, and 4 were characterized by spectroscopic means as well as their molecular structures were determined in the crystal.