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Structural and kinetic investigations of a Tc(III)/Tc(II) redox couple. X-ray crystal structures of trans-(Tc/sup II/(DPPE)/sub 2/Cl/sub 2/) and trans-(Tc/sup III/(DPPE)/sub 2/Cl/sub 2/)NO/sub 3/ x HNO/sub 3/, where DPPE = 1,2-bis(diphenylphosphino)ethane

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00293a035· OSTI ID:6236253
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The components of a reversible Tc(III/II) redox couple have been characterized by single-crystal x-ray analysis and the crystal parameters are reported. Oxidation of the Tc(II) complex to the Tc(III) form causes a shortening of the Tc-Cl bond by 0.105 (2) /angstrom/, consistent with the ionic nature of this interaction. Conversely, oxidation from Tc(II) to Tc(III) causes a lengthening of the Tc-P bond by 0.072 (2) /angstrom/, consistent with the domination of this interaction by ..pi..-back-bonding from Tc to P. The magnitudes of these bond length changes are used to predict the inner-sphere reorganization barrier to electron transfer of the trans-Tc(DPPE)/sub 2/Cl/sub 2//sup +/0/ couple to be only ca. 2.6 kcal/mol. Preliminary kinetic studies in nonaqueous media confirm that trans-(Tc/sup II/(DPPE)/sub 2/X/sub 2/) (X = Cl, Br) complexes are facile electron-transfer partners for a variety of 1-equiv oxidants. The rate of reduction of ((en)/sub 2/Co(S(CH/sub 2/C/sub 6/H/sub 4/CH/sub 3/)CH/sub 2/CH/sub 2/NH/sub 2/))/sup 3 +/ by trans-(Tc/sup II/(DPPE)/sub 2/Cl/sub 2/) in acetonitrile (25/degrees/C; ..mu.. = 0.10 M) is 3.0 (7) x 10/sup 4/ M/sup -1/ s/sup -1/. 56 references, 1 figure, 6 tables.

Research Organization:
Univ. of Cincinnati, OH (USA)
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
6236253
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:20; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400400* -- Electrochemistry
ALKANES
AROMATICS
CHEMICAL REACTIONS
CHLORINE COMPOUNDS
COMPLEXES
DATA
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HYDROCARBONS
INFORMATION
NITRATES
NITROGEN COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
OXYGEN COMPOUNDS
REDOX REACTIONS
TECHNETIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES