title: A carbene-carbene complex equilibrium.
abstract: Phenylchlorocarbene, generated by laser flash photolysis of phenylchlorodiazirine, formed highly stable pi-type complexes with 1,3,5-trimethoxybenzene in pentane. The carbene and carbene complexes were in equilibrium. We measured the equilibrium constant (K = 1264 M(-1) at 294 K) and, from its temperature dependence, extracted the associated thermodynamic parameters: DeltaH(o) = -7.1 kcal/mol, DeltaS(o) = -10.2 eu, and DeltaG(o) = -4.1 kcal/mol. The carbene complexes were characterized by UV-vis spectroscopy and computational analysis.
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, USA. moss@rutchem.rutgers.edu
authors.forename: Robert A
authors.initials: RA
authors.lastname: Moss
authors.forename: Lei
authors.initials: L
authors.lastname: Wang
authors.forename: Christina M
authors.initials: CM
authors.lastname: Odorisio
authors.forename: Karsten
authors.initials: K
authors.lastname: Krogh-Jespersen
mesh_terms: D003198:Computer Simulation; D003978:Diazomethane / Q000031:analogs & derivatives / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D013816:Thermodynamics
chemical_list: C030011:carbene; D003978:Diazomethane; D008697:Methane