Abstract
A dicationic PdII dimer, bis{2-[(diisopropylphosphanyl)methyl]quinoline-8-thiolato}palladium(II) bis(hexafluoridoantimonate) dichloromethane monosolvate, [Pd2(C32H42N2P2S2)](SbF6)2·CH2Cl2, containing a 2-[(diisopropylphos-phanyl)methyl]quinoline-8-thiolate pincer ligand, was isolated and its crystal structure determined. The title compound crystallizes in the ortho-rhom-bic space group Pbca. A dimeric structure is formed by bridging coordination of the S atoms. The geometry of the butterfly-shaped Pd2S2 core is bent, with a hinge angle of 108.0 (1)° and a short Pd⋯Pd distance of 2.8425 (7) Å. These values are the lowest measured compared to ten dicationic dimers with a Pd2S2 core featuring sulfur atoms embedded in a chelating ligand. One of the two hexa-fluorido-anti-monate anions is disordered over two sets of positions with site-occupancy factors of 0.711 (5) and 0.289 (5). The crystal structure is stabilized by many C-H⋯F and C-H⋯π inter-actions, forming a supra-molecular network.
Highlights
A dicationic PdII dimer, bis{2-[(diisopropylphosphanyl)methyl]quinoline-8thiolato}palladium(II) bis(hexafluoridoantimonate) dichloromethane monosolvate, [Pd2(C32H42N2P2S2)](SbF6)2ÁCH2Cl2, containing a 2-[(diisopropylphosphanyl)methyl]quinoline-8-thiolate pincer ligand, was isolated and its crystal structure determined
The geometry of the butterfly-shaped Pd2S2 core is bent, with a hinge angle of 108.0 (1) and a short PdÁ Á ÁPd distance of 2.8425 (7) A. These values are the lowest measured compared to ten dicationic dimers with a Pd2S2 core featuring sulfur atoms embedded in a chelating ligand
The crystal structure is stabilized by many C—HÁ Á ÁF and C—HÁ Á Á interactions, forming a supramolecular network
Summary
The stereoelectronic properties of transition-metal complexes can be finely modulated thanks to the ligands introduced on the metal coordination sphere, and this plays a fundamental role in organometallic chemistry. The central M—X bond is enforced by the coordination of two peripheral donor groups (D), and the chelating rigid nature of the monoanionic DXD pincer ligand bestows a unique balance between stability and reactivity. This has led to spectacular catalytic developments, including with pincer complexes based on Pd, a transition metal that occupies a central place in organometallic catalysis. As far as Pd is concerned, the main topology of the used monoanionic pincer ligands consists of an aryl central moiety featuring two coordinating side arms, as illustrated in Fig. 1 (model I) These complexes have been successfully applied to C—C or C—X bond-forming catalytic transformations. For each PNSPd fragment, besides the two bridging S atoms, the Pd atom is coordinated by one N atom and one P atom, completing a tetracoordinate sphere that deviates
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