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Title: Dual Coordination Modes of Ethylene-Linked NP2 Ligands in Cobalt(II) and Nickel(II) Iodides
Award ID(s):
0802907
NSF-PAR ID:
10040904
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Inorganic Chemistry
Volume:
50
Issue:
20
ISSN:
0020-1669
Page Range / eLocation ID:
10213 to 10224
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. 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.

     
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