The unique synthesis and reactivity of [(PNP*)NiH] complexes (,), based on metal-ligand cooperation (MLC), are presented (PNP* = deprotonated PNP ligand, R = Pr, Bu). Unexpectedly, the dearomatized complexes , were obtained by reduction of the dicationic complexes [(PNP)Ni(MeCN)](BF) with sodium amalgam or by reaction of the free ligand with Ni(COD). Complex reacts with CO via MLC, to give a rare case of a distorted-octahedral PNP-based pincer complex, the Ni(0) complex . Complexes , also react with CO via MLC to form a rare example of η binding of CO to nickel, complexes ,. An unusual CO cleavage process by complex , involving C-O and C-P cleavage and C-C bond formation, led to the Ni-CO complex and to the new complex [(PPrNCO)Ni(P(O)Pr)] (). All complexes have been fully characterized by NMR and X-ray crystallography.
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| http://dx.doi.org/10.1021/acs.organomet.8b00160 | DOI Listing |
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