Synthesis, spectroscopic and electrochemical investigations of a tetrathiamacrocycle and its copper(II) and nickel(II) complexes

• Published in: Journal of coordination chemistry Vol. 58; no. 3; pp. 209 - 215
• Main Authors: Prasad, Rajendra, Thankachan, P. P., Bansal, Vipin Kumar
• Format: Journal Article
• Language: English
• Published: Taylor & Francis Group 15-02-2005
• Subjects: Copper; Cyclic voltammetry; Maleonitrile dithiolate; Nickel; Ruthenium adduct; Tetrathiamacrocycle
• ISSN: 0095-8972; 1029-0389
• DOI: 10.1080/0095897042000327897

A new tetrathiomacrocycle possessing four peripheral pendant cyano groups has been synthesized in high yield by the metal-templated cyclization of Na
2
S
2
C
2
(CN)
2
and 1,3-dichloropropane in refluxing DMF followed by demetalation. The initially formed complexes [Ni{(CN)
4
[14]eneS
4
}]Cl
2
(1) and [CuCl
2
{(CN)
4
[14]eneS
4
}] (2) underwent demetalation upon reaction with CN
−
or H
2
S, respectively. Both 1 and 2 reacted with [CpRu(PPh
3
)
2
Cl] to form cationic dinuclear complexes 3 and 4, which were isolated as PF
salts. All complexes, as well as the metal-free tetrathiamacrocycle, were characterized by IR, electronic and
1
H NMR spectroscopy. Redox characteristics of the complexes were investigated using cyclic voltammetry.