Bis(1,2,3‐thiadiazole)s as Precursors in the Synthesis of Bis(alkynethiolate)gold(I) Derivatives

Abstract

The cleavage of bis(1,2,3‐thiadiazole)s in the presence of strong bases in situ gives bis(alkynethiolate)s, which provide bis(alkynethiolate)gold(I) derivatives with the general formula [Au2(S–C≡C–spacer–C≡C–S)L2] (L = monophosphanes; spacer = none, 1,4‐C6H4, 1,3‐C6H4, 2,7‐C15H12 and 3,5‐C7H7N). The dinuclear structure was confirmed by X‐ray diffraction studies of the complexes (PPN)2[Au2(S–C≡C–C≡C–S)(C6F5)2] and [Au2{3,5‐(S–C≡C)2–C7H7N}(PPh3)2] {PPN = bis(triphenylphosphane)iminium}. The use of diphosphanes gives complexes with higher nuclearity and cyclic structures.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Ruthenium complexes of 4,4′-bi-1,2,3-thiadiazole and azoimine ligands: syntheses, crystallography, and electrochemical studies

“…The 4,4 0 -bi-1,2,3-thiadiazole (btd) ligand used in this study was prepared according to a modified literature procedure [6]. The structural formulas of these ligands were confirmed by 1 H NMR and elemental analysis.…”

“…Ethyl carbazate was prepared by a procedure [11]. 4,4 0 -bi-1,2,3-Thiadiazole (btd) was prepared by following a procedure [6] with a small modification, using a light-protected system, since the btd ligand is not stable in the presence of light, and using ethanol as a polar protic solvent with a weak acetic acid as a catalyst as described briefly below. The synthesis and the physical characterization of the azoimine ligands (Azo) have been previously described [7].…”

“…The effects of the substituents on these ligands on the electronic properties of the ruthenium center have been studied [7][8][9][10]. In this study, we extend our work to prepare a new family of mixed-ligand ruthenium complexes of the type trans-[Ru II (btd)(Azo)Cl 2 ] ({Azo = PhN = NC(COMe) = NC 6 HY, where Y = H (a), Me (b), OMe (c), Cl (d) or Br (e)} and btd = 4,4 0 -bi-1,2,3-thiadiazole) to study the effects of the p-excessive 4,4 0 -bi-1,2,3-thiadiazole chelating ligand and the substituent Y on the electronic properties of the ruthenium center.…”

“…These compounds have been used to prepare a variety of low-valence mononuclear complexes involving coordination through the N(2)-nitrogen [5]. Several mononuclear and binuclear alkynethiolate complexes have also been prepared by base cleavage of thiadiazole or bis(thiadiazole) ligands [6].…”

Molecular packing and morphological stability of dihydro-indeno[1,2-b]fluorenes in the context of their substitution pattern

“…26,27 Following this reaction sequence, the terephthalic ester 1 was saponied and the resulting terephthalic acid 3 subsequently cyclized to the diketone 4 using sulfuric acid. 28 The diketone 4 was reduced to the dihy-droindenouorene 5 in a Wolff-Kishner reaction 28 and aerwards alkylated using a reaction protocol by Lardíes et al 29 The synthesis of the mixed substituted dihydroindeno-uorene derivatives was achieved starting from 2-bromo uorene 8 (Scheme 2). In a sequenced one-pot Miyaura borylation/ Suzuki-Miyaura cross-coupling reaction cascade the corresponding uorenyl pinacole boronate ester was generated in situ, which aerwards was reacted with 2-bromomethylbenzoate 9 leading to 2-uorenyl-methylbenzoate 10.…”