Abstract
A linear free-energy relationship exists between the half-wave potentials of the (II/I) couples of Ni(diphosphine)2 complexes and the hydride donor ability (ΔG°H -) of the corresponding [HNi(diphosphine)2]+ complexes. A similar correlation is observed between the half-wave potentials of the (I/O) couples of Ni(diphosphine)2 complexes and the pKa values (or ΔG°H +) 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, ΔG°H+, ΔG°H·, and ΔG°H-, for this class of nickel complexes. The molecular structures of Ni(Et2PCH2CH2 PPh2)2 and Ni(Ph2PCHCHPPh2)2 were determined by single-crystal X-ray diffraction studies.
| Original language | English |
|---|---|
| Pages (from-to) | 1832-1839 |
| Number of pages | 8 |
| Journal | Organometallics |
| Volume | 20 |
| Issue number | 9 |
| Publication status | Published - Apr 30 2001 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
Free-energy relationships between the proton and hydride donor abilities of [HNi(diphosphine)2]+ complexes and the half-wave potentials of their conjugate bases. / Berning, Douglas E.; Miedaner, Alex; Curtis, Calvin J.; Noll, Bruce C.; Rakowski DuBois, Mary C.; DuBois, Daniel L.
In: Organometallics, Vol. 20, No. 9, 30.04.2001, p. 1832-1839.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Free-energy relationships between the proton and hydride donor abilities of [HNi(diphosphine)2]+ complexes and the half-wave potentials of their conjugate bases
AU - Berning, Douglas E.
AU - Miedaner, Alex
AU - Curtis, Calvin J.
AU - Noll, Bruce C.
AU - Rakowski DuBois, Mary C.
AU - DuBois, Daniel L
PY - 2001/4/30
Y1 - 2001/4/30
N2 - A linear free-energy relationship exists between the half-wave potentials of the (II/I) couples of Ni(diphosphine)2 complexes and the hydride donor ability (ΔG°H -) of the corresponding [HNi(diphosphine)2]+ complexes. A similar correlation is observed between the half-wave potentials of the (I/O) couples of Ni(diphosphine)2 complexes and the pKa values (or ΔG°H +) 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, ΔG°H+, ΔG°H·, and ΔG°H-, for this class of nickel complexes. The molecular structures of Ni(Et2PCH2CH2 PPh2)2 and Ni(Ph2PCHCHPPh2)2 were determined by single-crystal X-ray diffraction studies.
AB - A linear free-energy relationship exists between the half-wave potentials of the (II/I) couples of Ni(diphosphine)2 complexes and the hydride donor ability (ΔG°H -) of the corresponding [HNi(diphosphine)2]+ complexes. A similar correlation is observed between the half-wave potentials of the (I/O) couples of Ni(diphosphine)2 complexes and the pKa values (or ΔG°H +) 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, ΔG°H+, ΔG°H·, and ΔG°H-, for this class of nickel complexes. The molecular structures of Ni(Et2PCH2CH2 PPh2)2 and Ni(Ph2PCHCHPPh2)2 were determined by single-crystal X-ray diffraction studies.
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UR - http://www.scopus.com/inward/citedby.url?scp=0035972358&partnerID=8YFLogxK
M3 - Article
VL - 20
SP - 1832
EP - 1839
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 9
ER -