Monomeric, one- and two-dimensional networks incorporating (2,6-Me2C6H3S)2Pb building blocks

Abstract

The amine coordination of lead(II) has been examined through the preparation and structural analysis of Lewis base adducts of bis(thiolato)lead(II) complexes. Reaction of Pb(OAc)(2) with 2,6-dimethylbenzenethiol affords (2,6-Me(2)C(6)H(3)S)(2)Pb (6) in high yield. The solubility of 6 in organic solvents allows for the preparation of the 1:2 Lewis acid-base adduct [(2,6-Me(2)C(6)H(3)S)(2)Pb(py)(2)](7), and 1:1 adducts [(2,6-Me(2)C(6)H(3)S)(2)Pb(micro(2)-bipy)](infinity](8) and [(2,6-Me(2)C(6)H(3)S)(2)Pb(micro(2)-pyr)](infinity)(9)(where py = pyridine, bipy = 4,4'-bipyridyl and pyr = pyrazine) from reaction with an excess of the appropriate amine. In contrast to 7, reaction of (C(6)H(5)S)(2)Pb (1) with pyridine afforded the 2:1 adduct [(C(6)H(5)S)(4)Pb(2)(py)](infinity)(10). Compounds were characterized via elemental analysis, FT-IR, solution (1)H and (13)C[(1)H](6) NMR spectroscopy, and X-ray crystallography (7-10). The structures of 7-9 show the thiolate groups occupying two equatorial positions and two amine nitrogen atoms occupying axial coordination sites, yielding distorted see-saw coordination geometries, or distorted trigonal bipyramids if an equatorial lone pair on lead is considered. The absence of intermolecular contacts in 7 and 8 result in monomeric and one-dimensional polymeric structures, respectively. Weak Pb...S intermolecular contacts in 9 result in the formation of a two-dimensional macrostructure. In contrast, the structure of , shows extensive intermolecular Pb...S interactions, resulting in five- and six-coordinate bonding environments for lead(II), and a complex polymeric structure in the solid state. This demonstrates the ability of the 2,6-dimethylphenylthiolate ligand to limit intermolecular lead-sulfur interactions, while allowing the axial coordination of amine Lewis base ligands.

catena-Poly[[bis(pyridine)lead(II)]bis(μ-pentafluorobenzenethiolato)]

“…The corresponding bis-pyridine adduct (I) ( equatorial site is presumably occupied by the stereochemically active lone pair of Pb II . This is a similar bonding motif to that observed for (2,6-Me 2 C 6 H 3 S) 2 Pb × 2py (Appleton et al, 2004), but shows some subtle structural differences. The Pb -N bond distances in (I) [Pb-N1 = 2.643 7, Pb-N2 = 2.637 (7) Å] are significantly shorter than those in (2,6-…”

“…Lead(II) thiolates tend to form polymeric structures in the solid state via intermolecular PbÁ Á ÁS interactions, see: Davidovich et al (2010) and references therein; Eichhö fer (2005). However, the bonding environment at lead and the degree of intermolecular bonding may be altered via the introduction of Lewis base ligands that occupy metal coordination sites, see: Appleton et al (2004); Briand et al (2007). It has been shown that [(F 5 C 6 S) 2 Pb] n exhibits a three-dimensional framework structure containing hexacoordinated Pb II atoms (Fleischer et al, 2006).…”

Structural variation in ethylenediamine and -diphosphine adducts of (2,6-Me2C6H3S)2Pb: a single crystal X-ray diffraction and 207Pb solid-state NMR spectroscopy study

“…In light of this, we previously reported the preparation of the 2,6-dimethylphenylthiolate (2,6-Me 2 C 6 H 3 S) 2 Pb (1), which shows an increased solubility in organic solvents over the alkyl-and unsubstituted arylthiolate (RS) 2 Pb analogues. 26 Reaction of 1 with pyridine ( py) yielded the 1 : 2 adduct (2,6-Me 2 C 6 H 3 S) 2 Pb( py) 2 (2), which is monomeric and exhibits no intermolecular Pb-S contacts. 26 Further, bridging Lewis base ligands 4,4′-bipyridyl (bipy) and pyrazine ( pyr) afforded the 1 : 1 coordination polymers [(2,6-Me 2 C 6 H 3 S) 2 Pb(L)] 4 [L = bipy (3), pyr (4)].…”

Synthesis, electrochemical properties and reactivity of [Fe(η5-C5H4PPh2)2]Pt(benzenethiolate)2 complexes: X-ray crystal structure of [Fe(η5-C5H4PPh2)2]Pt(SC6HF4)2

“…The (dppf)Pt(BzT) 2 complexes [13] were synthesized by the reaction of (dppf)PtCl 2 with monothiols such as 2,3,5,6-tetrafluorobenzenethiol ((TFBT)H) and 3,5-dimethylbezenethiol ((DMBT)H), and with a lead derivative (Pb(BT) 2 ) [14], as shown in Scheme 1. The (dppf)Pt(BT) 2 complex prepared using Pb(BT) 2 is chemically and spectroscopically identical with that prepared by using benzenethiol [6].…”