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Electronic and Structural Variations of a Nickel(0) N-Heterocyclic Phosphenium Complex in Comparison to Group 10 Analogues. | LitMetric
The bonding interactions and electronic structure of a diphosphine pincer ligand featuring an N-heterocyclic phosphenium/phosphido (NHP) central moiety with nickel are explored. Treating Ni(COD) with the pincer ligand [PPP]Cl in the presence of a two-electron phosphine donor ligand PMe generates chlorophosphine complex (PPP)Ni(PMe) (). The cationic Ni complex [(PPP)Ni(PMe)][BPh] () can be prepared by subsequent halide abstraction from with NaBPh. The assignment of as a Ni/NHP complex, based on analysis of structural parameters and computational investigations, lies in contrast to its previously reported group 10 M/NHP (M = Pd, Pt) analogues. The activation of O-H bonds across the Ni-P bond is demonstrated by the addition of isopropanol to afford the metal hydride species [(PPP)Ni(PMe)(H)][BPh] (). Notably, the installation of a P-H bond in the NHP unit by treatment of with LiAlH yields (PPP)Ni(PMe) (). The ambiphilic nature of the P-H bond was demonstrated through reactivity studies of P-H bond cleavage in comparison to a Pd analogue (PPP)Pd(PPh) ().
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