title: Synthesis, structure and theoretical investigation into a homoleptic tris(dithiolene) tungsten.
abstract: A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S'}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2-hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S'}tungsten with the molecular formula of C54H54O12S6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a=12.756(2) Å, b=21.560(3) Å, c=24.980(4) Å and β=103.998(3)°. Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.
authors.affiliation: Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia.
authors.forename: Khuzaimah
authors.initials: K
authors.lastname: Arifin
authors.affiliation: Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia.
authors.forename: Lorna Jeffery
authors.initials: LJ
authors.lastname: Minggu
authors.affiliation: Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia; Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, University of Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia.
authors.forename: Wan Ramli Wan
authors.initials: WR
authors.lastname: Daud
authors.affiliation: School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia.
authors.forename: Bohari M
authors.initials: BM
authors.lastname: Yamin
authors.affiliation: School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia.
authors.forename: Rusli
authors.initials: R
authors.lastname: Daik
authors.affiliation: Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia; School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia. Electronic address: mbkassim@ukm.my.
authors.forename: Mohammad B
authors.initials: MB
authors.lastname: Kassim
mesh_terms: D018360:Crystallography, X-Ray; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013457:Sulfur Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D014414:Tungsten / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D013457:Sulfur Compounds; D014414:Tungsten
keywords: DFT; Dithiolene; Homoleptic; Non-innocent; Tungsten