Synthesis and Structural Characterisation of Diorganotin(IV) and Diphenyllead(IV) Complexes of Pyrimidine‐2‐thionate Derivatives

Abstract

The reaction between the ligands 4‐(trifluoromethyl)pyrimidine‐2‐thione (4‐CF3pymSH) and 6‐methyl‐4‐(trifluoromethyl)pyrimidine‐2‐thione (6‐Me‐4‐CF3pymSH) and the corresponding diorganotin(IV) dichloride [R2SnCl2] (R = Me, tBu or Ph) or diphenyllead(IV) dichloride in the presence of triethylamine yields the diorganotin(IV) complexes [R2Sn(4‐CF3pymS)2] and [R2Sn(6‐Me‐4‐CF3pymS)2] or diorganolead(IV) complexes [Ph2Pb(4‐CF3pymS)2] and [Ph2Pb(6‐Me‐4‐CF3pymS)2], respectively. The compounds have been characterised by microanalysis, mass spectrometry and by IR and Mössbauer spectroscopy and, in the case of the compound that was sufficiently soluble, by 1H, 13C, 119Sn and 207Pb NMR spectroscopy. The compounds [Me2Sn(4‐CF3pymS)2] (1), [Ph2Sn(4‐CF3pymS)2] (2), [Ph2Sn(6‐Me‐4‐CF3pymS)2] (5), [tBu2Sn(6‐Me‐4‐CF3pymS)2] (6), [Ph2Pb(4‐CF3pymS)2] (7) and [Ph2Pb(6‐Me‐4‐CF3pymS)2] (8) have also been characterised by X‐ray diffraction. The X‐ray crystal structures show that the metal centre in all these complexes is in a distorted octahedral environment with bonds to two carbon atoms from the aryl or alkyl substituents and to sulfur and heterocyclic nitrogen atoms from the pyrimidine derivative, which acts a (κ2‐N,S) chelating ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Synthesis, antimicrobial activity and molecular docking of di‐ and triorganotin (IV) complexes with thiosemicarbazide derivatives

“…In complex 6 the Sn1‐N3 bond distance, although long, is in the range of other compounds found in the literature, so the ligand coordinates to the metal in a bidentate manner, giving rise to the formation of a four‐member chelate ring, coordination mode that has been previously observed in related complexes . The metal is in a C 3 NS coordination environment (Figure ) with a value of the τ 5 parameter of 0.68, corresponding to a strongly distorted trigonal bipyramid environment (τ 5 = 0 for square‐pyramid and τ 5 = 1 for trigonal bipyramid) .…”

Heptacoordinated diphenyllead; hexa- and pentacoordinated triphenyllead and tin compounds derived from 5H-benzimidazo[1,2-c]quinazoline-6-thione

“…11. Distorted geometry in a reported hexacoordinated lead compound [22]. Angles values are N-Pb-N 161.9°, S-Pb-S 83.96°and C-Pb-C 142.8°.…”

“…The nitrogen and sulfur chelate forms a four-membered ring, giving a pentacyclic fused system bearing a pentacoordinated tin atom. This type of chelate has been reported for tin and lead compounds [20][21][22][23][24][25]. The 119 Sn spectrum of compound 3 dissolved in DMSO-d 6 showed a signal at À231.7 ppm, characteristic of a hexacoordinate tin atom, Scheme 3, as a result of DMSO coordination [26].…”

Binuclear Copper(I) Compounds with N‐Heterocyclic Thiolate and Diphosphane Ligands: Effects of Thiolate Ligands on Solid‐State Molecular Structures and Luminescence Properties

“…Thiol or thiolate ligands, owing to their ability of the S‐donor atom to bridge different metal centers and to yield complexes with variable nuclearity and structural complexity, appear to be a very interesting class of ligands for the synthesis of photoluminescent Cu I complexes with diverse multinuclear molecular architectures. In particular, N‐heterocyclic thiol/thiolate comprises a subclass of S‐donor ligands that can adopt a variety of coordination modes, acting either in their neutral or anionic forms: (a) in a monodentate fashion (through the S atom, or through the N atom), (b) as N,S‐chelating ligands, (c) as binuclear bridging ligands (through the S atom,, or the N and S atoms,) or (d) as trinuclear bridging ligands . Heteroleptic Cu I complexes incorporating S‐donor, N‐heterocyclic thiol/thiolate ligands, in combination with other types of ligands, such as P‐donor arylphosphanes, halides or N‐donor polypyridines, have been reported to exhibit diverse structures and interesting photophysical properties .…”