title: Electron attachment to Ni(PF(3))(4) and Pt(PF(3))(4).
abstract: An experimental study has been made of thermal electron attachment to the transition-metal trifluorophosphine complexes Ni(PF(3))(4) and Pt(PF(3))(4) using a flowing-afterglow Langmuir-probe apparatus. Both complexes are efficient at electron attachment, although the rate constants are somewhat less than collisional. The rate constant for electron attachment to Ni(PF(3))(4) is 1.9 x 10(-7) cm(3) s(-1) at room temperature, about a factor of 2 less than collisional. The activation energy is 39+/-5 meV for the attachment reaction. The rate constant for electron attachment to Pt(PF(3))(4) is 5.4 x 10(-8) cm(3) s(-1) at room temperature, and the activation energy is 84+/-8 meV. For both complexes, a PF(3) ligand is lost on electron attachment, and only the M(PF(3))(3)(-) ion is observed in the negative-ion mass spectrum. Density functional calculations were carried out on Ni(PF(3))(4) and various fragments in order to describe the thermochemistry of the attachment reaction.
authors.affiliation: Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Bedford, MA 01731-3010, USA. jeff@prtc.net
authors.forename: Jeffrey F
authors.initials: JF
authors.lastname: Friedman
authors.forename: Thomas M
authors.initials: TM
authors.lastname: Miller
authors.forename: Jessica K
authors.initials: JK
authors.lastname: Friedman-Schaffer
authors.forename: A A
authors.initials: AA
authors.lastname: Viggiano
authors.forename: G K
authors.initials: GK
authors.lastname: Rekha
authors.forename: Amy E
authors.initials: AE
authors.lastname: Stevens