Predictable and unpredictable reactions between 4,4′-dipyridyldisulfide and phosphonodithioato/dithiophosphato NiII complexes: novel coordination polymers and the unique example of 4,4′-dipyridyltrisulfide

Abstract

The reactions between dpds and the phosphonodithioato and dithiophosphato NiII complexes [Ni(MeOpdt)2] (1), [Ni(EtOpdt)2] (2), and [Ni((EtO)2PS2)2] (3) yielded the novel coordination polymers (1·dpds)∞, (2·dpts)∞, and (3·dps)∞, featuring three different spacers ensuing from in situ chemical rearrangement of the starting dpds reagent (dpds, 4,4′-dipyridyldisulfide; dps, 4,4′-dipyridylmonosulfide; dpts, 4,4′-dipyridyltrisulfide)

Solvothermal heterocyclic disulfide/CuX2 (X = Cl, ClO4) reactions involving dynamic S–S and C–S bond cleavage

“…In this burgeoning area, in situ metal/heterocyclic disulfide reactions have received much interest, largely because of their diverse S-S reactions [3] as exemplified by the most extensively studied bis(2-pyrimidinyl)disulfide (Pym 2 S 2 ), bis(2-pyridinyl)disulfide (2-dpds), and bis(4-pyridinyl)disulfide (4-dpds). Metal/heterocyclic disulfide reactions can readily occur, either in ambient solution [4][5][6][7][8][9][10] or under solvothermal conditions [11][12][13][14][15][16][17][18][19]. They are subject to a range of reaction parameters including metal salts, solvent, temperature, and even reaction time.…”

Construction of metal–organic replica of sqc1121 network based on a multifunctional ligand via solvothermal in situ disulfide cleavage reaction

“…Furthermore, ligands with the S-S bond have attracted considerable interest in coordination chemistry due to the following considerations: (i) its potential relevance in biological systems, (ii) its twisted conformation and axial chirality which shows the potential ability to generate M and P enantiomers in chiral crystal engineering, and (iii) the facile cleavage of the S-S bond to result in diversiform in situ ligand reactions. So far, some ligands with the disulfide bond are widely used and a few examples of in situ ligand generation involving cleavage of the S-S bond are reported [13][14][15][16]. For example, the starting reagent 4,4′-dipyridyldisulfide could be converted to pyridine-4-thiolate [13], 1-(4-pyridyl)-4-thiopyridine [14], 4,4′-dipyridylsulfide [15], or 4,4′-dipyridyltrisulfide [16], respectively.…”

“…So far, some ligands with the disulfide bond are widely used and a few examples of in situ ligand generation involving cleavage of the S-S bond are reported [13][14][15][16]. For example, the starting reagent 4,4′-dipyridyldisulfide could be converted to pyridine-4-thiolate [13], 1-(4-pyridyl)-4-thiopyridine [14], 4,4′-dipyridylsulfide [15], or 4,4′-dipyridyltrisulfide [16], respectively. Recently, Wang and his co-workers have reported two new complexes {[Cu(6-sinic)(4,4′-bipy) 0.5 ]·CH 3 OH· H 2 O} n (6-sinic= 6-sulfinatonicotinate) and [Cd 2 (L) 2 (phen)] n (L =6-mercaptonicotinate), in which the corresponding ligand is generated from 6,6′-dithiodinicotinic acid (H 2 cpds) through in situ reactions [17].…”

Diverse reactions of S–S function under metal-mediated and metal-free thermolysis conditions

“…Moreover, by thorough control of reaction parameters, C-S and S-S scissions may partly occur in 4-dpds, resulting in attractive supramolecular architectures involved with mixed ligands of 4-dpds and 4-dps [4]. Besides it, even in normal solution reaction, extrusion or insertion of one sulfur atom may take place in the S-S function of 4-dpds to give 4-dps or 4,4 0 -dipyridinetrisulfine (4-dpts) [5]. Irrespective of increasing research enthusiasm on reactions of organic disulfide compounds with metal ions, nevertheless, the unambiguous reactivity of disulfide in the absence of metal ions, to the best of our knowledge, is rarely noticed.…”