10.1021/acs.organomet.8b00759.s001
Pei-Hua Zhao
Pei-Hua
Zhao
Meng-Yuan Hu
Meng-Yuan
Hu
Jian-Rong Li
Jian-Rong
Li
Zhong-Yi Ma
Zhong-Yi
Ma
Yan-Zhong Wang
Yan-Zhong
Wang
Jiao He
Jiao
He
Yu-Long Li
Yu-Long
Li
Xu-Feng Liu
Xu-Feng
Liu
Influence of Dithiolate Bridges on the Structures
and Electrocatalytic Performance of Small Bite-Angle PNP-Chelated
Diiron Complexes Fe<sub>2</sub>(μ-xdt)(CO)<sub>4</sub>{κ<sup>2</sup>‑(Ph<sub>2</sub>P)<sub>2</sub>NR} Related to [FeFe]-Hydrogenases
American Chemical Society
2019
2 NR
diiron
FT-IR
3 NMe 2
xdt
Fe 2 S 2 complexes
complexes 1 b
UV
CH 2
SCH 2 CH 2 S
NMR
Ph 2 P
edt complexes 2
chelating PNP ligands
adt NPh
CH 2 CHMe 2
single-crystal X-ray diffraction analysis
carbonyl substitution reactions
adt NPh complexes 1
2019-01-03 20:04:50
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Influence_of_Dithiolate_Bridges_on_the_Structures_and_Electrocatalytic_Performance_of_Small_Bite-Angle_PNP-Chelated_Diiron_Complexes_Fe_sub_2_sub_-xdt_CO_sub_4_sub_sup_2_sup_Ph_sub_2_sub_P_sub_2_sub_NR_Related_to_FeFe_-Hydrogenases/7544861
As
a further exploration of the asymmetrically substituted diiron
models for the active site of [FeFe]-hydrogenases, two new types of
small bite-angle aminodiphosphine [(Ph<sub>2</sub>P)<sub>2</sub>NR;
denoted as PNP in this study]-chelated diiron <i>N</i>-phenyl-aza-
and ethanedithioate complexes Fe<sub>2</sub>(μ-xdt)(CO)<sub>4</sub>{κ<sup>2</sup>-(Ph<sub>2</sub>P)<sub>2</sub>NR} (<b>1a</b>–<b>1e</b>) and (<b>2a</b>–<b>2e</b>), respectively, were successfully synthesized by the carbonyl
substitution reactions of all-carbonyl diiron complexes Fe<sub>2</sub>(μ-xdt)(CO)<sub>6</sub> (xdt = SCH<sub>2</sub>N(Ph)CH<sub>2</sub>S (adt<sup>NPh</sup>) and SCH<sub>2</sub>CH<sub>2</sub>S (edt)) with
PNP (PNP = (Ph<sub>2</sub>P)<sub>2</sub>NR, R = CMe<sub>3</sub>, CH<sub>2</sub>CHMe<sub>2</sub>, (CH<sub>2</sub>)<sub>3</sub>Me, (CH<sub>2</sub>)<sub>3</sub>Si(OEt)<sub>3</sub>, and (CH<sub>2</sub>)<sub>3</sub>NMe<sub>2</sub>) in the presence of Me<sub>3</sub>NO·2H<sub>2</sub>O or UV irradiation. All the new complexes obtained above have been well characterized
by elemental analysis, FT-IR, NMR spectroscopy, and particularly for <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2d</b> by
single-crystal X-ray diffraction analysis. By comparison, <sup>31</sup>P{<sup>1</sup>H} NMR and X-ray crystallographic studies have clearly
revealed that the change of the dithiolate bridge from adt<sup>NPh</sup> to edt has a significant influence on the coordination geometry
of the chelating PNP ligands in Fe<sub>2</sub>S<sub>2</sub> complexes,
in which the basal–basal configuration in the adt<sup>NPh</sup> complexes <b>1a</b>–<b>1e</b> is favorable whereas
the apical–basal conformation in the edt complexes <b>2a</b>–<b>2e</b> is main. In addition, the electrochemical
properties of complexes <b>1b</b> and <b>2b</b> as a pair
of representative counterparts are evaluated and compared by cyclic
voltammetry in the absence and presence of HOAc as a proton source,
indicating that they are found to be electrocatalytically active.