Abstract
[M(diphosphine)2]2+ complexes (where M = Ni and Pt) react with hydrogen in the presence of bases to form the corresponding hydrides, [HM(diphosphine)2]+. In seven cases, equilibria have been observed from which the hydride donor ability (ΔG°H-) of the hydrides can be calculated. For six of these complexes, the ΔG°H- values calculated using heterolytic activation of hydrogen are compared with those based on thermodynamic cycles using pKa measurements and electrochemical half-wave potentials. The agreement between these two methods is good (within 1 kcal/mol). The reactivity of the various [M(diphosphine)2]2+ complexes toward hydrogen parallels their measured hydride acceptor abilities.
| Original language | English |
|---|---|
| Pages (from-to) | 1918-1925 |
| Number of pages | 8 |
| Journal | Journal of the American Chemical Society |
| Volume | 124 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - Mar 6 2002 |
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Measurement of the hydride donor abilities of [HM(diphosphine)2]+ complexes (M = Ni, Pt) by heterolytic activation of hydrogen. / Curtis, Calvin J.; Miedaner, Alex; Ellis, William W.; DuBois, Daniel L.
In: Journal of the American Chemical Society, Vol. 124, No. 9, 06.03.2002, p. 1918-1925.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Measurement of the hydride donor abilities of [HM(diphosphine)2]+ complexes (M = Ni, Pt) by heterolytic activation of hydrogen
AU - Curtis, Calvin J.
AU - Miedaner, Alex
AU - Ellis, William W.
AU - DuBois, Daniel L
PY - 2002/3/6
Y1 - 2002/3/6
N2 - [M(diphosphine)2]2+ complexes (where M = Ni and Pt) react with hydrogen in the presence of bases to form the corresponding hydrides, [HM(diphosphine)2]+. In seven cases, equilibria have been observed from which the hydride donor ability (ΔG°H-) of the hydrides can be calculated. For six of these complexes, the ΔG°H- values calculated using heterolytic activation of hydrogen are compared with those based on thermodynamic cycles using pKa measurements and electrochemical half-wave potentials. The agreement between these two methods is good (within 1 kcal/mol). The reactivity of the various [M(diphosphine)2]2+ complexes toward hydrogen parallels their measured hydride acceptor abilities.
AB - [M(diphosphine)2]2+ complexes (where M = Ni and Pt) react with hydrogen in the presence of bases to form the corresponding hydrides, [HM(diphosphine)2]+. In seven cases, equilibria have been observed from which the hydride donor ability (ΔG°H-) of the hydrides can be calculated. For six of these complexes, the ΔG°H- values calculated using heterolytic activation of hydrogen are compared with those based on thermodynamic cycles using pKa measurements and electrochemical half-wave potentials. The agreement between these two methods is good (within 1 kcal/mol). The reactivity of the various [M(diphosphine)2]2+ complexes toward hydrogen parallels their measured hydride acceptor abilities.
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U2 - 10.1021/ja0116829
DO - 10.1021/ja0116829
M3 - Article
VL - 124
SP - 1918
EP - 1925
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 9
ER -