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According to DFT analysis on (PPP)NiCl (1) and (PPP)NiOPh (4), significant nickel d-orbital character can be found in HOMOs, while dx2-y2 character was found in the LUMO, suggesting that both complexes possess a d8 Ni(II) center. In fact, the HOMO for 1 and HOMO-1 for 4 possess the significant contribution of a central phosphorus atom indicating the presence of a Ni(II)-bound electron-rich phosphide moiety in both species; see Supporting Information. In addition, the nickel's oxidation state and the electronic nature of the central phosphorus atom in 1-5 and 7 can be evaluated by comparing their 31P NMR and XRD data; see Table S7.
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Product DMC (∼10%) generated from the reaction was detected by 1H NMR spectroscopy in toluene with internal standard 1,1,2,2-tetrachloroethane by comparison with an authentic sample of DMC; see Supporting Information.
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