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 |
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Authors: | Nanhai Singh Bandana Singh Michael GB Drew |
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Institution: | a Department of Chemistry, Banaras Hindu University, Varanasi 221 005, UP, India b Chemistry Department, IIT Kanpur, Kanpur 208 016, India c Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, UK |
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Abstract: | Two new complex salts of the form (Bu4N)2Ni(L)2] (1) and (Ph4P)2Ni(L)2] (2) and four heteroleptic complexes cis-M(PPh3)2(L) M = Ni(II) (3), Pd(II) (4), L = 4-CH3OC6H4SO2NCS2] and cis-M(PPh3)2(L′) M = Pd(II) (5), Pt(II) (6), L′ = C6H5SO2NCS2] 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(PPh3)2(SH)2, 4a was also obtained with the synthesis of 4. The NiS4 and MP2S2 core in the complex salts and heteroleptic complexes are in the distorted square-plane whereas in the trans complex, 4a the centrosymmetric PdS2P2 core is perforce square planar. X-ray crystallography revealed the proximity of the ortho phenyl proton of the PPh3 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 σrt values ∼10−5 S cm−1 show semi-conductor behaviors. The palladium and platinum complexes show photoluminescence properties in solution at room temperature. |
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Keywords: | Dithiocarbimate Complex salts Heteroleptic Semi-conductor Photoluminescence |
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