Studies of synthesis, structural features of Cu(i) thiophene-2-thiocarboxylates and unprecedented desulfurization of Cu(ii) thiocarboxylate complexes

Abstract

Thiophene-2-thiocarboxylate complexes of Cu(I), [(Ph(3)P)(2)Cu(SCOth)] (1) and H[(Ph(3)P)(2)Cu(SCOth)(2)] (2) (where th = thiophene) were synthesized and characterized structurally by X-ray crystallography. Electronic absorption and emission spectral properties of the two compounds have been studied. Cu(II) complexes, [(TMEDA)Cu(SCOth)(2)] (3b) and [(Phen)Cu(SCOth)(2)] (4a) (where TMEDA = tetramethylethylenediamine; Phen = 1,10-phenanthroline) were prepared and characterized by spectroscopic measurements. 3b and 4a underwent desulfurization under ambient conditions readily yielding the corresponding carboxylate complexes [(TMEDA)Cu(O(2)Cth)(2)] (3a) and [(Phen)Cu(O(2)Cth)(2)·H(2)O] (4b). 3a and 4b have been characterized crystallographically.

Synthesis and characterization of metallo-supramolecular polymers from thiophene-based unimers bearing pybox ligands

“…21 Despite extensive work in our laboratory with tridentate 2,2 0 :6 0 2 00 -terpyridine-4-yl units, [22][23][24][25][26][27] the decision to synthesize ditopic unimers with another tridentate ligand -2,6-bis(oxazolyl)pyridine (pybox)has been taken into account. The main reasons behind this decision were as follows: (i) oxazoline complexes have a large application potential in microelectronics and also as catalytic systems (especially Ru-based pybox derivatives); [28][29][30][31][32] (ii) pybox based ligands allow an easy derivatization through attaching substituents at the 4-position of the pyridine rings (in this case, optical isomerism is introduced into the pybox motif, allowing further tailoring of the prepared systems); (iii) pybox derivatives exhibit much better solubility in organic solvents, which is an important parameter in MSP processing. 33 Therefore, all these abovementioned potential advantages of the bis(oxazolines), in combination with the thiophene based central blocks, bring their own benets such as the possibility of band gap tuning, high absorption coefficients, charge transport properties, etc.…”

Copper(I) Complexes with Anionic Acylthio‐ or Acylselenourea Ligands and N‐Heterocyclic Carbenes or Phosphanes

“…Nevertheless, the combination of 31 P NMR spectroscopy and electrospray mass spectrometry clearly demonstrate, that in solution these complexes undergo ligand exchange processes. Bhattacharya has observed similar behaviour in a copper(I) bis(triphenylphosphane) complex containing a thiophene‐2‐thiocarboxylato ligand . This compound displays three sharp singlets at 43, 36 and 29 ppm as well as a broad resonance at –3 ppm in its 31 P NMR spectrum at room temperature.…”

Studies of structural diversity due to inter-/intra-molecular hydrogen bonding and photoluminescent properties in thiocarboxylate Cu(i) and Ag(i) complexes

“…Reagents and general procedures All the solvents were dried according to standard procedures and distilled before use. [(PPh 3 ) 2 Cu(SCOth)], 7 thiophene-2-thiocarboxylic acid, furan-2-thiocarboxylic acid (FuCOSH), 8 bis-(triphenylphosphine)copper(I) nitrate 9 and bis(triphenylphosphine)silver(I) nitrate 10 were prepared by reported procedures. Thiobenzoic acid, thioacetic acid, 2-mercapto-2-thiazoline (MT) and 2-mercaptobenzimidazole (MB) were purchase from Aldrich and used as received.…”

“…5a,b,6d Recently, we have observed that Cu(II) complexes of thiocarboxylate ligands undergo spontaneous desulfurization where as those of Cu(I) are quite stable. 7 Thiocarboxylate ligand (having both S and O donor sites) form primary bonding with the metal through S atom while the O remains free which can be exploited for hydrogen bonding. In view of these facts we thought it will be worthwhile to study the structural features of copper and silver complexes containing heterocyclic thioamides as well as thiocarboxylates.…”