Synthesis and characterization of 1,8-dithia-4,11-diazacyclotetradecane

Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO2 reduction and enhanced proton reduction

“…In order to better understand the importance of sulfur within the many known metalloenzymes and to allow for comparison with the electrocatalytic system 1, we synthesized the sulfur-containing cyclam derivative 1,8-dithia-4,11-diazacyclotetradecane (dithiacyclam) 2 (Scheme 3 and Scheme S1). 30 The reaction of the N 2 S 2 -donor ligand 2 with Ni(ClO 4 ) 2 •6H 2 O in acetonitrile subsequently afforded a dark purple crystalline solid in 87 % yield (Scheme 3). The metalation of 2 was confirmed by electrospray-ionization mass spectrometry (ESI-MS), revealing two characteristic peaks at m/z = 292 and 391 for the [Ni(dithiacyclam)] + and the [Ni(dithiacyclam)(ClO 4 )] + fragments.…”

“…1,8-dithia-4,11diazacyclotetradecane (dithiacyclam) 2 was synthesized according to a literature-known procedure with minor alterations. 30 spectra using a 31 element solid state germanium detector (Canberra), over an energy range of 8133 -8895 eV. A Co filter of three absorption lengths was used to reduce scatter and maintain detector linearity.…”

Electrochemical CO2 and Proton Reduction by a Co(dithiacyclam) Complex

“…Prior to their use, all solvents were dried and degassed according to standard methods. 1,8‐Dithiacyclam‐4,11‐diazacyclotetradecane (dithiacyclam) L4 was synthesized according to literature‐known procedures . Mass spectra were obtained with a Bruker Daltonics Esquire 6000 instrument.…”

Macrocyclic Assembly: A Dive into the Pecking Order and Applied Aspects of Multitalented Metallomacrocycles

“…These macrocycles which contain varying combinations of aza (N), oxa (O) phospha (P), and sulfa (S) ligating atoms can be tailored to accommodate specific metal ions by the fine-tuning of the ligand design features, such as the macrocyclic hole size, nature of the ligand donors, donor set, donor array, ligand conjugation, ligand substitution, number and sizes of the chelate rings, ligand flexibility, and nature of the ligand backbone. A large amount of data has been 2 International Journal of Inorganic Chemistry published on macrocyclic ligands containing only nitrogen, only sulphur, or both as donor atoms, namely, tetraaza [12], thiadiaza [13], thiatriaza [14], dithiadiaza [15,16], or dithiatriaza [17]. However, there is scarce information on thiatetraaza compounds.…”