American Chemical Society
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A Coordination Polymer of Nickel(II) Based on a Pentadentate N, S, and O Donor Ligand

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journal contribution
posted on 1996-08-14, 00:00 authored by Dawn C. Goodman, Patrick J. Farmer, Marcetta Y. Darensbourg, Joseph H. Reibenspies
The synthesis, structural characterization, and electrochemical properties of a NiII complex derived from the template reaction of N,N‘-bis(2-mercaptoethyl)-1,5-diazacyclooctane nickel(II), Ni-1, with ICH2CO2Na are described. Blue N-(3-thiabutyl)-N‘-(3-thiapentanoate)-1,5-diazacyclooctanenickel(II)iodide, [(tbtp-daco)Ni][I], [5]I, contains NiII in an octahedral environment with N2S2O2 donor atoms; one oxygen is from an adjacent [(tbtp-daco)Ni] ion and has the same distance to NiII as the intramolecular oxygen, resulting in a coordination polymer. Complex [5]I·H2O, C13H27N2O3S2NiI, crystallizes in the orthorhombic space group Pbca with a = 10.898(3), b = 18.103(5), c = 19.020(5), and Z = 8. The extent to which the polymer is retained in solution is counterion dependent, which influences redox properties (accessibility of NiI and NiIII).