Synthesis, X-ray crystal structures and properties of complex salts and sterically crowded heteroleptic complexes of group 10 metal ions with aromatic sulfonyl dithiocarbimates and triphenylphosphine ligand

Abstract

Two new complex salts of the form (Bu 4N) 2[Ni(L) 2] ( 1) and (Ph 4P) 2[Ni(L) 2] ( 2) and four heteroleptic complexes cis-M(PPh 3) 2(L) [M = Ni(II) ( 3), Pd(II) ( 4), L = 4-CH 3OC 6H 4SO 2N CS 2] and cis-M(PPh 3) 2(L′) [ M = Pd(II) ( 5), Pt(II) ( 6), L′ = C 6H 5SO 2N CS 2] were prepared and characterized by elemental analyses, IR, 1H, 13C and 31P NMR and UV–Vis spectra, solution and solid phase conductivity measurements and X-ray crystallography. A minor product trans-Pd(PPh 3) 2(SH) 2, 4a was also obtained with the synthesis of 4. The NiS 4 and MP 2S 2 core in the complex salts and heteroleptic complexes are in the distorted square-plane whereas in the trans complex, 4a the centrosymmetric PdS 2P 2 core is perforce square planar. X-ray crystallography revealed the proximity of the ortho phenyl proton of the PPh 3 ligand to Pd(II) showing rare intramolecular C–H⋯Pd anagostic binding interactions in the palladium cis- 5 and trans- 4a complexes. The complex salts with σ rt values ∼10 −5 S cm −1 show semi-conductor behaviors. The palladium and platinum complexes show photoluminescence properties in solution at room temperature.