| Title: |
Increasing Ligand Denticity and Stability for a Water Oxidation Electrocatalyst using P(V) as Connecting Element |
| Authors: |
Saeedifard, Farzaneh; Breyer, Colton J.; Chi Cao, Thomas; Kamdar, Jayneil M.; Kerkhof, Jake; Smith, Diane K.; Cooksy, Andrew L.; Rheingold, Arnold L.; Moore, Curtis E.; Gu, Jing; Grotjahn, Douglas B. |
| Contributors: |
Office of Science |
| Source: |
ChemCatChem ; volume 16, issue 12 ; ISSN 1867-3880 1867-3899 |
| Publisher Information: |
Wiley |
| Publication Year: |
2024 |
| Collection: |
Wiley Online Library (Open Access Articles via Crossref) |
| Description: |
Carboxylate complexes have risen to prominence in the field of water oxidation catalysis. Here for the first time we use the higher valence of phosphinates [P(V)] relative to that of carboxylates [C(IV)] to increase ligand denticity. We describe the synthesis and characterization of a new dianionic pentadentate ligand, bcpq 2− that contains a tridentate 2,2’‐bipyridine‐6‐carboxylato moiety, in addition to a 6’‐phosphinato substituent that acts as fourth ligand and bears a side arm containing a quinoline, the fifth ligand. The new bcpq ligand allows formation of [Ru(II)(bcpq)(L)] ( 2 a – b , L=picoline or isoquinoline) and in preliminary results, of a Co(II) complex. NMR spectroscopy, X‐ray diffraction, cyclic voltammetry, differential pulse and square wave voltammetry were used to characterize 2 a – b , with 2 b being characterized more extensively as a catalyst. Bulk electrolysis over 15 h at pH 7 was also used, showing that 2 b gave 100±5 % faradaic efficiency and remained completely homogeneous, whereas 1 b was no longer homogeneous; this comparison conclusively shows the advantage of the added denticity in the electrocatalytic context. Replacing carboxylate with P(V) phosphinate with an added arm may be used in other ligand systems to enhance the durability of homogeneous catalysts. |
| Document Type: |
article in journal/newspaper |
| Language: |
English |
| DOI: |
10.1002/cctc.202301644 |
| Availability: |
https://doi.org/10.1002/cctc.202301644; https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/cctc.202301644 |
| Rights: |
http://creativecommons.org/licenses/by/4.0/ |
| Accession Number: |
edsbas.AC9D0CC6 |
| Database: |
BASE |