TY - JOUR
T1 - Interplay between β-diimino and β-diketiminato ligands in nickel complexes active in the proton reduction reaction
AU - Gimbert Suriñach, Carolina
AU - Llobet Dalmases, Antoni
N1 - Publisher Copyright:
© 2022 The Authors. All rights reserved.
PY - 2022/10/24
Y1 - 2022/10/24
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85139550822&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/c3cd3d0b-1de3-37f4-b1aa-339c2dba2383/
U2 - 10.1021/acs.inorgchem.2c02150
DO - 10.1021/acs.inorgchem.2c02150
M3 - Article
C2 - 36196853
SN - 0020-1669
VL - 61
SP - 16639
EP - 16649
JO - INORGANIC CHEMISTRY
JF - INORGANIC CHEMISTRY
IS - 42
ER -