title: Rearrangement in a tripodal nitroxide ligand to modulate the reactivity of a Ti-F bond.
abstract: The tripodal nitroxide ligand [(2-(t)BuNO)C6H4CH2)3N](3-) (TriNOx(3-)) binds the Ti(IV) cation and prevents inner-sphere coordination of chloride in the complex [Ti(TriNOx)]Cl (1). The ligand undergoes an η(2)-NO to κ(1)-O rearrangement to enable a fluoride ion to bind in the related complex Ti(TriNOx)F (2). Computational and reactivity studies demonstrated that the ligand rearrangement contributed to the enthalpy change in the transfer of a fluoride anion.
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Michael A
authors.initials: MA
authors.lastname: Boreen
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Justin A
authors.initials: JA
authors.lastname: Bogart
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Carroll
authors.affiliation: P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Schelter