title: Mono-, bi-, and trinuclear CuII-Cl containing products based on the tris(2-pyridylmethyl)amine chelate derived from copper(I) complex dechlorination reactions of chloroform.
abstract: The ligand TMPA (tris(2-pyridylmethyl)amine) and its copper complexes have played a prominent role in recent (bio)inorganic chemistry studies; the copper(I) complex [CuI(TMPA)(CH3CN)]+ possesses an extensive dioxygen reactivity, and it is also known to effect the reductive dechlorination of substrates such as dichloromethane and benzyl and allyl chlorides. In this report, we describe a set of new analogues of TMPA, ligand 6TMPAOH, binucleating Iso-DO, and trinucleating SYMM. Copper(I) complexes with these ligands and a previously described binucleating ligand DO react with chloroform, resulting in reductive dechlorination and production of [CuIIx(L)Clx]x+ (x = 1, 2, or 3). X-ray crystal structures of [CuII(6TMPAOH)Cl]PF6, [CuII2(Iso-DO)Cl2](PF6)2, [CuII2(DO)Cl2](PF6)2, and [Cu3(SYMM)Cl3](PF6)3 are presented, and the compounds are also characterized by UV-vis and EPR spectroscopies as well as cyclic voltammetry. The steric influence of a pyridyl 6-substituent (in the complexes with 6TMPAOH, Iso-DO, and SYMM) on the solid state and solution structures and redox potentials are compared and contrasted to those chlorocopper(II) complexes with a pyridyl 5'-substituent (in [CuII2(DO)Cl2](PF6)2 and in [CuII(TMPA)Cl]+). Some insights into the reductive dechlorination process have been obtained by using 2H NMR spectroscopy in following the reaction of [Cu2(Iso-DO)(CH3CN)2](PF6)2 with CDCl3, in the presence or absence of a radical trap, 2,4-di-tert-butylphenol.
authors.affiliation: Department of Chemistry, The Johns Hopkins University, 3400 N. Charles Street, Baltimore, Maryland 21218, USA.
authors.forename: Baldo
authors.initials: B
authors.lastname: Lucchese
authors.forename: Kristi J
authors.initials: KJ
authors.lastname: Humphreys
authors.forename: Dong-Heon
authors.initials: DH
authors.lastname: Lee
authors.forename: Christopher D
authors.initials: CD
authors.lastname: Incarvito
authors.forename: Roger D
authors.initials: RD
authors.lastname: Sommer
authors.forename: Arnold L
authors.initials: AL
authors.lastname: Rheingold
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Karlin
mesh_terms: D002614:Chelating Agents / Q000737:chemistry*; D002725:Chloroform / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D008024:Ligands; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry
chemical_list: D002614:Chelating Agents; D006843:Hydrocarbons, Chlorinated; D008024:Ligands; D009942:Organometallic Compounds; D003300:Copper; D002725:Chloroform; D010100:Oxygen