skip to main content


Title: Dearomatization of the PCP Pincer Ligand in a Re V Oxo Complex
NSF-PAR ID:
10072491
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Chemistry - A European Journal
Volume:
24
Issue:
52
ISSN:
0947-6539
Page Range / eLocation ID:
p. 13754-13757
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
  2. Abstract

    Three binuclear species [LCoIII2(μ‐Pz)2](ClO4)3(1), [LNiII2(CH3OH)2Cl2]ClO4(2), and [LZnII2Cl2]PF6(3) supported by the deprotonated form of the ligand 2,6‐bis[bis(2‐pyridylmethyl) amino‐methyl]‐4‐methylphenol were synthesized, structurally characterized as solids and in solution, and had their electrochemical and spectroscopic behavior established. Species13had their water reduction ability studied aiming to interrogate the possible cooperative catalytic activity between two neighboring metal centers. Species1and2reduced H2O to H2effectively at an applied potential of −1.6 VAg/AgCl, yielding turnover numbers of 2,820 and 2,290, respectively, after 30 minutes. Species3lacked activity and was used as a negative control to eliminate the possibility of ligand‐based catalysis. Pre‐ and post‐catalytic data gave evidence of the molecular nature of the process within the timeframe of the experiments. Species1showed structural, rather than electronic cooperativity, while species2displayed no obvious cooperativity. DFT methods complemented the experimental results determining plausible mechanisms.

     
    more » « less