In:
Applied Organometallic Chemistry, Wiley, Vol. 34, No. 1 ( 2020-01)
Abstract:
Six new O‐ alkyldithiophosphate nickel complexes with dcpf ligand, [(dcpf)Ni(S 2 P{O}OR)] (dcpf = 1,1′‐bis (dicyclohexylphosphino)ferrocene, R = CH 3 ( 1 ), CH 3 CH 2 ( 2 ), Ph ( 3 ), 4‐MeC 6 H 4 ( 4 ), PhCH 2 ( 5 ) and PhCH 2 CH 2 ( 6 )), have been synthesized by the treatment of dcpf with ((RO) 2 PS 2 ) 2 Ni in satisfactory yields. These complexes were characterized by elemental analysis, spectroscopy (FTIR, UV–vis, 1 H, 13 C, and 31 P NMR), thermogravimetric analysis and single crystal X‐ray diffraction. The nickel atom in 1 , 2 ·CH 2 Cl 2 , 3 ·CH 2 Cl 2 , 4 ·2CH 2 Cl 2 ·THF, and 2( 5 )·hexane adopts a slightly distorted square‐planar coordination environment finished by two phosphorus atoms of dcpf ligand and two sulfur atoms of O‐ alkyldithiophosphate ligand. Furthermore, the electrochemical properties for complexes 1 – 6 were also investigated by cyclic voltammetry. With the addition of 120 mM trifluoroacetic acid (TFA), the turnover frequency (TOF) values for 1 – 6 are estimated to be 1243.83, 1046.54, 1331.71, 2545.29, 1899.03, and 1191.37 s −1 , with the overpotential (η) values of 0.62, 0.58, 0.71, 0.67, 0.60, and 0.56 V, respectively. The result of electrochemical studies indicates that all complexes can be used as efficient molecular eletrocatalysts for the reduction of protons to hydrogen in the presence of TFA in MeCN.
Type of Medium:
Online Resource
ISSN:
0268-2605
,
1099-0739
Language:
English
Publisher:
Wiley
Publication Date:
2020
detail.hit.zdb_id:
1480791-9