Abstract
The reaction of zerovalent nickel compounds with white phosphorus (P4) is a barely explored route to binary nickel phosphide clusters. Here, we show that coordinatively and electronically unsaturated N‐heterocyclic carbene (NHC) nickel(0) complexes afford unusual cluster compounds with P1, P3, P5 and P8 units. Using [Ni(IMes)2] [IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene], electron‐deficient Ni3P4 and Ni3P6 clusters have been isolated, which can be described as superhypercloso and hypercloso clusters according to the Wade–Mingos rules. Use of the bulkier NHC complexes [Ni(IPr)2] or [(IPr)Ni(η6‐toluene)] [IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene] affords a closo‐Ni3P8 cluster. Inverse‐sandwich complexes [(NHC)2Ni2P5] (NHC=IMes, IPr) with an aromatic cyclo‐P5 − ligand were identified as additional products.
Highlights
Die Reaktion von Nickel(0)-Verbindungen mit weißem Phosphor (P4) ist eine kaum erforschte Syntheseroute für binäre Nickelphosphidcluster
Nichtsdestotrotz ist 4 unseren Wissens nach das erste Beispiel eines solchen P8-Gerüsts in einer isolierten, molekularen Verbindung.[4]
Das X-BandEPR-Spektrum von 3 b (Abbildung 6) in Toluol-Glas bei 20 K zeigt ein axiales Signalmuster für ein S = 1=2-System mit Hyperfeinkopplung zu allen fünf Phosphoratomen
Summary
Die Reaktion von Nickel(0)-Verbindungen mit weißem Phosphor (P4) ist eine kaum erforschte Syntheseroute für binäre Nickelphosphidcluster. Erfreulicherweise zeigte das 31P{1H}-NMRSpektrum der Reaktion von [Ni(IMes)2] mit P4 (0.5 3⁄4quiv.) in Toluol ein Hauptprodukt, welches zwei Signale in einem 1:1Verhältnis aufweist (Schema 1).
Sign-in/Register to view highlights & summary Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
