Tricarbonylrhenium(I) Complexes of Dinucleating Redox-Active
Pincer Ligands
Posted on 2018-03-08 - 18:52
Two homobimetallic tricarbonylrhenium(I)
complexes of new redox-active
dinucleating pincer ligands have been prepared to assess the impact
of spacer size on the first oxidation potentials with respect to mononucleating
analogues and on intramolecular electronic communication. The new
pincer ligands feature two tridentate NNN- sites
each composed of two pyrazolyl flanking donors and a diarylamido anchor
that are either directly linked (to form a central benzidene core,
H2(L1)) or linked via a para-phenylene
group (to form a para-terphenyldiamine core, H2(L2)). The bimetallic complexes of the deprotonated ligands,
[fac-Re(CO)3]2(μ-L1), 1, and [fac-Re(CO)3]2(μ-L2), 2, were fully characterized in solution
and the solid state including by single-crystal X-ray diffraction
for 1. The electrochemical properties of each depended
strongly on solvent and electrolyte. Complex 1 exhibits
two one-electron oxidations in all electrolyte-containing solutions
but with separations between first and second oxidation potentials,
ΔE1/2, between 119 and 316 mV depending
on conditions. On the other hand, cyclic voltammetry of 2 showed one two-electron oxidation in DMF with NBu4PF6 as an electrolyte but two one-electron oxidations with a
maximal separation in ΔE1/2 of 96
mV in CH2Cl2 with NBu4B(C6F5)4 as an electrolyte. The oxidized complexes 1n+ and 2n+ (n = 1, 2) were
prepared by chemical oxidation and were studied spectroscopically
(UV–vis/NIR, EPR). The mono-oxidized complex 1+ behaves as a Robin–Day Class III
species, while 2+ is a Robin–Day
Class II species that shows thermal valence trapping at 77 K by EPR
spectroscopy. As suggested from theoretical studies using DFT methods,
the oxidized complexes maintain considerable ligand radical character,
so their electronic structures can be formulated as (CO)3ReI(μ-Ln+)ReI(CO)3 (n = 1 or 2).
CITE THIS COLLECTION
DataCite
3 Biotech
3D Printing in Medicine
3D Research
3D-Printed Materials and Systems
4OR
AAPG Bulletin
AAPS Open
AAPS PharmSciTech
Abhandlungen aus dem Mathematischen Seminar der Universität Hamburg
ABI Technik (German)
Academic Medicine
Academic Pediatrics
Academic Psychiatry
Academic Questions
Academy of Management Discoveries
Academy of Management Journal
Academy of Management Learning and Education
Academy of Management Perspectives
Academy of Management Proceedings
Academy of Management Review
Gardinier, James R.; Hewage, Jeewantha S.; Bennett, Brian; Wang, Denan; Lindeman, Sergey V. (2018). Tricarbonylrhenium(I) Complexes of Dinucleating Redox-Active
Pincer Ligands. ACS Publications. Collection. https://doi.org/10.1021/acs.organomet.8b00013
or
Select your citation style and then place your mouse over the citation text to select it.
SHARE
Usage metrics
Read the peer-reviewed publication
AUTHORS (5)
JG
James R. Gardinier
JH
Jeewantha S. Hewage
BB
Brian Bennett
DW
Denan Wang
SL
Sergey V. Lindeman