title: Synthesis, spectral (IR, UV-Vis and variable temperature NMR) characterization and crystal structure of (N-benzyl-N-furfuryldithicarbamato-S,S')(thiocyanato-N)(triphenylphosphine)nickel(II).
abstract: Planar (N-benzyl-N-furfuryldithiocarbamato-S,S')(thiocyanato-N)(triphenylphospine)nickel(II), [Ni(bfdtc)(NCS)(PPh3)], (1) was prepared from bis(N-benzyl-N-furfuryldithiocarbamato-S,S')nickel(II), [Ni(bfdtc)2], (2) and characterized by elemental analysis, cyclic voltammetry, electronic, IR and variable temperature (1)H and (13)C NMR spectra. For complex 1, the thioureide vCN value is shifted to higher wavenumber compared to 2 and N(13)CS2 carbon signal observed for 1 is additionally shielded compared to the parent complex 2, suggesting increased strength of the thioureide bond due to the presence of the π-accepting phosphine. In the room temperature (13)C NMR spectrum of 1, two pseudo doublets are observed in the aliphatic region. Variable temperature (13)C NMR spectral studies suggest that the fast thiocyanate exchange appears to be responsible for the appearance of pseudo doublets. Single crystal X-ray structural analysis of 1 and 2 confirm the presence of four coordinated nickel in a distorted square planar arrangement with the NiS2PN and NiS4 chromophores, respectively. The NiS bonds are symmetric in 2 (2.1914(14) and 2.2073(13)Å). But significant asymmetry in NiS bond distances was observed in 1 (2.2202(8)Å and 2.1841Å). This observation clearly supports the less effective trans effect of SCN(-) over PPh3. Cyclic voltammetric studies revealed easier reduction of nickel(II) to nickel(I) in complex 1 compared to 2.
authors.affiliation: Department of Chemistry, Annamalai University, Annamalainagar, Tamil Nadu 608 002, India.
authors.forename: P
authors.initials: P
authors.lastname: Valarmathi
authors.affiliation: Department of Chemistry, Annamalai University, Annamalainagar, Tamil Nadu 608 002, India. Electronic address: sthirumaran@yahoo.com.
authors.forename: S
authors.initials: S
authors.lastname: Thirumaran
authors.affiliation: X-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India.
authors.forename: Lovely
authors.initials: L
authors.lastname: Sarmal
authors.affiliation: X-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India.
authors.forename: Rajni
authors.initials: R
authors.lastname: Kant
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005663:Furans / Q000138:chemical synthesis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D013861:Thiocyanates / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D005663:Furans; D009943:Organophosphorus Compounds; D013861:Thiocyanates; C061896:triphenylphosphine; D009532:Nickel
keywords: Crystal structure; Dithiocarbamate; Nickel(II); Variable temperature NMR spectra