Abstract
Reaction of the (1,4-diazabutadiene)bis(alkene)nickel(0) complexes (2,6-Me2Ph-dad)Ni(C2H4)2 and (2,6-Me2Ph-dad)Ni(η2,η2-C6H10) with ethyne gives the dinuclear nickelole complex [(2,6-Me2Ph-dad)Ni]2{σ2(1,4),η4(1–4)-C4H4} (2). A single-crystal X-ray structure study of 2·0.5 toluene (2a) reveals strongly distorted coordination geometries of the formally nickel(II) and nickel(O) centres. From the 1H and 13C NMR spectra of dissolved 2 it can be concluded that a rapid dynamic process proceeds in solution even at −80°C (!), presumably a rotation of the (2,6-Me2Ph-dad)Ni0 fragment around the bonding axis to the nickelacyclopentadiene component. At higher temperatures a further dynamic process takes place, leading to an exchange of the bonding environments of the nickel atoms. Die (1,4-Diazabutadien)bis(alken)nickel(0)-Komplexe (2,6-Me2Ph-dad)Ni(C2H4)2 und (2,6-Me2Ph-dad)Ni(η2,η2-C6H10 reagieren mit Ethin zu dem zweikernigen Nickelol-Komplex [(2,6-Me2Ph-dad)Ni]2{σ2(1,4),η4(1–4)-C4H4} (2). Kristallines 2·0.5 Toluol (2a) zeigt laut Röntgenstrukturanalyse stark verzerrte Koordinationsgeometrien der formalen Nickel(II)- und Nickel(0)-Zentren. Allerdings lassen die 1H- und 13C-NMR-Spektren von gelöstem 2 auf einen bei −80°C raschen (!) dynamischen Prozess schließen, bei dem vermutlich das (2,6-Me2Ph-dad)Ni0-Fragment urn die Bindungsachse zur Nickelacyclopentadien-Komponente rotiert. Bei h:oherer Temperatur ist ein weiterer dynamischer Prozefß festzustellen, der einen Austausch der Bindungsverhältnisse der Nickel-Zentren bewirkt.
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