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The nickel PNP pincer complex (   i  Pr PNP)NiPh (   i  Pr PNP = κ P ,κ N ,κ P -N(CH 2 CH 2 P  i  Pr 2 ) 2 ) was prepared by reacting (   i  Pr PNP)NiBr with PhMgCl or deprotonating [(   i  Pr PN H P)NiPh]Y (   i  Pr PN H P = κ P ,κ N ,κ P -HN(CH 2 CH 2 P  i  Pr 2 ) 2 ; Y = Br, PF 6 ) with KO  t  Bu. The byproducts of the PhMgCl reaction were identified as [(   i  Pr PN H P)NiPh]Br and (   i  Pr PNP')NiPh (   i  Pr PNP' = κ P ,κ N ,κ P -N(CH=CHP  i  Pr 2 )(CH 2 CH 2 P  i  Pr 2 )). The methyl analog (   i  Pr PNP)NiMe was synthesized from the reaction of (   i  Pr PNP)NiBr with MeLi, although it was contaminated with (   i  Pr PNP')NiMe due to ligand oxidation. Protonation of (   i  Pr PNP)NiX (X = Br, Ph, Me) with various acids, such as HCl, water, and MeOH, was studied in C 6 D 6 . Nitrogen protonation was shown to be the most favorable process, producing a cationic species [(   i  Pr PN H P)NiX] + with the NH moiety hydrogen-bonded to the conjugate base (i.e., Cl - , HO - , or MeO - ). Protonation of the Ni-C bond was observed at room temperature with (   i  Pr PNP)NiMe, whereas at 70 °C with (   i  Pr PNP)NiPh, both resulting in [(   i  Pr PN H P)NiCl]Cl as the final product. Protonation of (   i  Pr PNP)NiBr was complicated by site exchange between Br - and the conjugate base and by the degradation of the pincer complexes. Indene, which lacks hydrogen-bonding capability, was unable to protonate (   i  Pr PNP)NiPh and (   i  Pr PNP)NiMe, despite being more acidic than water and MeOH. Neutral and cationic nickel pincer complexes involved in this study, including (   i  Pr PNP')NiBr, (   i  Pr PNP)NiPh, (   i  Pr PNP')NiPh, (   i  Pr PNP)NiMe, [(   i  Pr PN H P)NiPh]Y (Y = Br, PF 6 , BPh 4 ), [(   i  Pr PN H P)NiPh] 2 [NiCl 4 ], [(   i  Pr PN H P)NiMe]Y (Y = Cl, Br, BPh 4 ), [(   i  Pr PN H P)NiBr]Br, and [(   i  Pr PN H P)NiCl]Cl, were characterized by X-ray crystallography.

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Roles of Hydrogen Bonding in Proton Transfer to κP,κN,κP-N(CH2CH2PiPr2)2-Ligated Nickel Pincer Complexes