Electron attachment to Ni(PF(3))(4) and Pt(PF(3))(4).
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.
Friedman
Jeffrey F
JF
Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Bedford, MA 01731-3010, USA. jeff@prtc.net
Miller
Thomas M
TM
Friedman-Schaffer
Jessica K
JK
Viggiano
A A
AA
Rekha
G K
GK
Stevens
Amy E
AE