title: Formation of the Vilsmeier-Haack complex: the performance of different levels of theory.
abstract: Because of discrepancies in the available experimental data, an extensive theoretical investigation of the formation of the Vilsmeier-Haack (VH) complex has been carried out. The barriers to complex formation calculated using eight different density functional methods (BLYP, B2-PLYP, B3LYP, B3PW91, MPW1K, M06-2X, and PBE1PBE), MP2, and extrapolation techniques (CBS-QB3, G3B3) with several basis sets (6 - 31 + G, 6 - 311++G, 6 - 311 + (3df,2p), aug-cc-pVDZ, and aug-cc-pVTZ) were compared with experimental data. For the overall reaction, MP2/aug-cc-pVDZ and M06-2X/6-31 + G(d,p) perform best compared to the CBS techniques. The results help clarify some open mechanistic questions.
authors.affiliation: Computer-Chemie-Centrum, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstrsse 25, 91052 Erlangen, Germany.
authors.forename: Gül Altınbaş
authors.initials: GA
authors.lastname: Ozpınar
authors.forename: Dieter E
authors.initials: DE
authors.lastname: Kaufmann
authors.forename: Timothy
authors.initials: T
authors.lastname: Clark
mesh_terms: D002625:Chemistry, Organic; D019281:Dimerization; D004126:Dimethylformamide / Q000737:chemistry*; D006860:Hydrogen Bonding; D007477:Ions / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008958:Models, Molecular; D017553:Phosphorus Compounds / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D007477:Ions; D017553:Phosphorus Compounds; D004126:Dimethylformamide; C013196:phosphoryl chloride