Synthesis, structure and physical properties of tetrabutylammonium salts of nickel complexes with the new ligand dcbdt=4,5-dicyanobenzene-1,2-dithiolate, [Ni(dcbdt)(2)](z-) (z = 0.4, 1, 2)

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abstract

The synthesis and characterization of the new aromatic ortho-dithiol, 4,5-dicyanobenzene-1,2-dithiol (3) is reported. This compound was used to prepare tetrabutylammonium salts of novel nickel complexes; the nickel(II) salt (nBu(4)N)(2)-[Ni(dcbdt)(2)] (4), the nickel(III) salt (nBu(4)N)(2)[Ni(debdt)(2)](2) (5), and the partially oxidized Ni-III/IV salt (nBu(4)N)(2)[Ni(dcbdt)(2)](5) (6). (dcbdt = 4,5-dicyanobenzene-1,2-dithiolate). The Ni-II complex presents a square-planar coordination geometry and is diamagnetic, while in the paramagnetic Ni-III complex the Ni(dcbdt)(2) units are strongly dimerized with the metal atom in a square-pyramidal coordination geometry and its magnetic susceptibility follows a singlet-triplet model with an antiferromagnetic coupling J = 897 K. The partially oxidized Ni-III/IV complex 6 presents a weakly temperature-dependent paramagnetism of 5-6 . 10(-4) emu/mol and a room-temperature electrical conductivity of 0.15 S/cm following a semiconducting regime.

keywords

METAL-COMPLEXES; CRYSTAL-STRUCTURE; MOLECULAR-METALS; CONDUCTORS; THERMOPOWER; DMIT; FE

subject category

Chemistry

authors

Simao, D; Alves, H; Belo, D; Rabaca, S; Lopes, EB; Santos, IC; Gama, V; Duarte, MT; Henriques, RT; Novais, H; Almeida, M

our authors

foto Helena Alves

Helena Alves

Principal Researcher

Groups

G1 - Porous Materials and Nanosystems

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Publication Details

type
Journal Article
year
2001
journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
publisher
WILEY-BLACKWELL
issn
1434-1948
issue
12
web of science article identifier
WOS:000172505300019

Journal Metrics (JCR 2019)

Journal Impact Factor
2.529
Journal Impact Factor (5 yrs)
2.284
category normalized journal percentile
65.556

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