Interplay between β-diimino and β-diketiminato ligands in nickel complexes active in the proton reduction reaction

Carolina Gimbert Suriñach*, Antoni Llobet Dalmases*

*Corresponding author for this work

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Two Ni complexes are reported with κ4-P2N2 β-diimino (BDI) ligands with general formula [Ni(XBDI)](BF4)2, where BDI is N-(2-(diphenylphosphaneyl)ethyl)-4-((2-(diphenylphosphaneyl)ethyl)imino)pent-2-en-2-amine and X indicates the substituent in the α-carbon intradiimine position, X = H for 1(BF4)2 and X = Ph for 2(BF4)2. Electrochemical analysis together with UV-vis and NMR spectroscopy in acetonitrile and dimethylformamide (DMF) indicate the conversion of the β-diimino complexes 12+ and 22+ to the negatively charged β-diketiminato (BDK) analogues (1-H)+ and (2-H)+ via deprotonation in DMF. Moreover, further electrochemical and spectroscopy evidence indicate that the one-electron reduced derivatives 1+ and 2+ can also rapidly evolve to the BDK (1-H)+ and (2-H)+ respectively, via hydrogen gas evolution through a bimolecular homolytic pathway. Finally, both complexes are demonstrated to be active for the proton reduction reaction in DMF at Eapp = -1.8 V vs Fc+/0, being the active species the one-electron reduced derivative of 1-H and 2-H.
Original languageEnglish
Pages (from-to)16639-16649
Number of pages11
JournalINORGANIC CHEMISTRY
Volume61
Issue number42
DOIs
Publication statusPublished - 24 Oct 2022

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