Free-energy relationships between the proton and hydride donor abilities of [HNi(diphosphine)(2)](+) complexes and the half-wave potentials of their conjugate bases

Citation
De. Berning et al., Free-energy relationships between the proton and hydride donor abilities of [HNi(diphosphine)(2)](+) complexes and the half-wave potentials of their conjugate bases, ORGANOMETAL, 20(9), 2001, pp. 1832-1839
Citations number
41
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANOMETALLICS
ISSN journal
0276-7333 → ACNP
Volume
20
Issue
9
Year of publication
2001
Pages
1832 - 1839
Database
ISI
SICI code
0276-7333(20010430)20:9<1832:FRBTPA>2.0.ZU;2-J
Abstract
A linear free-energy relationship exists between the half-wave potentials o f the (II/I) couples of Ni(diphosphine)(2) complexes and the hydride donor ability (DeltaG(H)(o)(-)) of the corresponding [HNi(diphosphine)(2)](+) com plexes. A similar correlation is observed between the half-wave potentials of the (I/O) couples of Ni(diphosphine)(2) complexes and the pK(a) values ( or DeltaG(H)(o)(+)) of the corresponding [HNi(diphosphine)(2)](+) complexes . As a result, it is possible to use the potentials of these two couples to predict the free energies of all three Ni-H bond cleavage reactions, Delta G(H)(o)(+), DeltaG(H)(o)(.), and DeltaG(H)(o)(-), for this class of nickel complexes. The molecular structures of Ni(Et2PCH2CH2PPh2)(2) and Ni(Ph2PCHC HPPh2)(2) were determined by single-crystal Ii-ray diffraction studies.