Solvent-free mechanochemical synthesis of dithiophosphonic acids and corresponding nickel(II) complexes

Flexible Molecular Precursors for Selective Decomposition to Nickel Sulfide or Nickel Phosphide for Water Splitting and Supercapacitance

“…[Ni{S 2 P(OR)(4‐MeOC 6 H 4 )} 2 ] (R=H (1), C 3 H 7 (2)) : The synthesis of complexes 1 and 2 was carried out by slight modification of the established literature procedure . The procedure requires heating of P2S5 to reflux in anisole for six hours by using standard Schlenk techniques, cooling, and filtration to form (4‐C 6 H 4 OMeP(S)S) 2 , commonly referred to as the Lawesson's reagent (LR).…”

“…The complete molecule of 1 , 2 , and 3 has the two dithiophosphonate ligands coordinated to the Ni1 atom through the S1 and S2 atoms in a κ 2 :S,S′ coordination mode as shown in Figure . Furthermore, the anisyl moiety in 1 and 2 , and the phenetolyl moiety in 3 of the coordinated ligands are arranged in a trans configuration, which is similar to that observed in closely related structures . As a result, the metal center in all the compounds adopted a distorted square‐planar geometry with S‐Ni‐S bond angles between 81.820(4) and 180° (Table ).…”

“…Complex 1 crystallizes in the orthorhombic space group Pbca whereas complexes 2 and 3 crystallize in the triclinic space group P1 .Aperspective view of complexes 1, 2,a nd 3 is given in Figure2,w hereas Ta bles 1a nd 2g ive important X-ray crystallographic data and selected bond parameters, respectively. There has been ap revious report [18] of as imilar Ni II molecular structure as 1,t hough as ah ydrated ammonium salt. We present ab etter well-resolved model of the molecular structure of 2 earlier reported.…”

“…[Ni{S 2 P(OR)(4-MeOC 6 H 4 )} 2 ]( R = H( 1), C 3 H 7 (2)):T he synthesis of complexes 1 and 2 was carried out by slight modification of the established literature procedure. [18,36] The procedure requires heating of P2S5 to reflux in anisole for six hours by using standard Schlenk techniques, cooling, and filtration to form (4-C 6 H 4 OMeP(S)S) 2 ,c ommonly referred to as the Lawesson'sr eagent (LR). LR and water or alcohol [deionized H 2 O( 1)o rC 3 H 7 OH (2)] in the appropriate stoichiometric amounts were stirred in THF in an inert atmosphere until the cloudy mixture went clear.S toichiometric amounts of NiCl 2 ·6H 2 Ow ere added in solid form into the clear THF solutions, yielding immediate purple precipitates, which were filtered and washed with deionized water to remove any excess NiCl 2 ·6H 2 O.…”

Heterodimetallic Ferrocenyl Dithiophosphonate Complexes of Nickel(II), Zinc(II) and Cadmium(II) as Sensitizers for TiO2‐Based Dye‐Sensitized Solar Cells

“…In our ongoing work on phosphor‐1,1‐dithiolate complexes generally– and the dithiophosphonate class of complexes in particular– we turned our attention for the first time to the viability of multimetallic ferrocenyl dithiophosphonate complexes as low cost, high efficiency co‐sensitizers in DSSCs. We synthesized two new nickel(II) ( 1‐2 ), one zinc(II) ( 3 ) and one cadmium(II) ( 4 ) complex bearing the FcLR ligand.…”