Aggregation and Degradation of White Phosphorus Mediated by N‐Heterocyclic Carbene Nickel(0) Complexes. Issue 33 (3rd June 2020)

• Record Type: Journal Article
• Authors: Hierlmeier, Gabriele; Coburger, Peter; van Leest, Nicolaas P.; de Bruin, Bas; Wolf, Robert
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 33(2020)
• Page Start: 14148
• Page End: 14153
• Publication Date: 2020-06-03
• Subjects: cluster compounds -- nickel -- P4 activation -- phosphorus -- polyphosphides; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202004020
• Languages: English
• ISSNs: 1433-7851

Abstract

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 Ni3 P4 and Ni3 P6 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(η 6 ‐toluene)] [IPr=1, 3‐bis(2, 6‐diisopropylphenyl)imidazolin‐2‐ylidene] affords a closo ‐Ni3 P8 cluster. Inverse‐sandwich complexes [(NHC)2 Ni2 P5 ] (NHC=IMes, IPr) with an aromatic cyclo ‐P5 − ligand were identified as additional products. Abstract : Active nickel : Activation of white phosphorus (P4 ) by N‐heterocyclic carbene nickel(0) complexes affords binary nickel phosphorus cluster compounds. Both the degradation of P4 to P1 and P3 units and the aggregation to P5 and P8 moieties has been observed. The structures of the resulting Ni3 P4, Ni3 P6, and Ni3 P8 clusters can be understood with the Wade–Mingos electron‐counting rules.