Abstract
Treatment of the bis(diisopropylphosphino)pyridine iron dichloride, ( iPrPNP)FeCl2 (iPrPNP = 2,6-(iPr 2PCH2)2(C5H3N)), with 2 equiv of NaBEt3H under an atmosphere of dinitrogen furnished the diamagnetic iron(II) dihydride dinitrogen complex, (iPrPNP)FeH 2(N2). Addition of 1 equiv of PhSiH3 to ( iPrPNP)FeH2(N2) resulted in exclusive substitution of the hydride trans to the pyridine to yield the silyl hydride dinitrogen compound, (iPrPNP)FeH(SiH2Ph)N2, which has been characterized by X-ray diffraction. The solid-state structure established a distorted octahedral geometry where the hydride ligand distorts toward the iron silyl. Both (iPrPNP)FeH2(N2) and (iPrPNP)FeH(SiH2Ph)N2 form η2-dihydrogen complexes upon exposure to H2. The iron hydrides and the η2-H2 ligands are in rapid exchange in solution, consistent with the previously reported "cis" effect, arising from a dipole/induced dipole interaction between the two ligands. Taken together, the spectroscopic, structural, and reactivity studies highlight the relative electron-donating ability of this pincer ligand as compared to the redox-active aryl-substituted bis(imino)pyridines.
| Original language | English |
|---|---|
| Pages (from-to) | 7252-7260 |
| Number of pages | 9 |
| Journal | Inorganic Chemistry |
| Volume | 45 |
| Issue number | 18 |
| DOIs | |
| Publication status | Published - Sep 4 2006 |
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ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
Bis(diisopropylphosphino)pyridine iron dicarbonyl, dihydride, and silyl hydride complexes. / Trovitch, Ryan; Lobkovsky, Emil; Chirik, Paul J.
In: Inorganic Chemistry, Vol. 45, No. 18, 04.09.2006, p. 7252-7260.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Bis(diisopropylphosphino)pyridine iron dicarbonyl, dihydride, and silyl hydride complexes
AU - Trovitch, Ryan
AU - Lobkovsky, Emil
AU - Chirik, Paul J.
PY - 2006/9/4
Y1 - 2006/9/4
N2 - Treatment of the bis(diisopropylphosphino)pyridine iron dichloride, ( iPrPNP)FeCl2 (iPrPNP = 2,6-(iPr 2PCH2)2(C5H3N)), with 2 equiv of NaBEt3H under an atmosphere of dinitrogen furnished the diamagnetic iron(II) dihydride dinitrogen complex, (iPrPNP)FeH 2(N2). Addition of 1 equiv of PhSiH3 to ( iPrPNP)FeH2(N2) resulted in exclusive substitution of the hydride trans to the pyridine to yield the silyl hydride dinitrogen compound, (iPrPNP)FeH(SiH2Ph)N2, which has been characterized by X-ray diffraction. The solid-state structure established a distorted octahedral geometry where the hydride ligand distorts toward the iron silyl. Both (iPrPNP)FeH2(N2) and (iPrPNP)FeH(SiH2Ph)N2 form η2-dihydrogen complexes upon exposure to H2. The iron hydrides and the η2-H2 ligands are in rapid exchange in solution, consistent with the previously reported "cis" effect, arising from a dipole/induced dipole interaction between the two ligands. Taken together, the spectroscopic, structural, and reactivity studies highlight the relative electron-donating ability of this pincer ligand as compared to the redox-active aryl-substituted bis(imino)pyridines.
AB - Treatment of the bis(diisopropylphosphino)pyridine iron dichloride, ( iPrPNP)FeCl2 (iPrPNP = 2,6-(iPr 2PCH2)2(C5H3N)), with 2 equiv of NaBEt3H under an atmosphere of dinitrogen furnished the diamagnetic iron(II) dihydride dinitrogen complex, (iPrPNP)FeH 2(N2). Addition of 1 equiv of PhSiH3 to ( iPrPNP)FeH2(N2) resulted in exclusive substitution of the hydride trans to the pyridine to yield the silyl hydride dinitrogen compound, (iPrPNP)FeH(SiH2Ph)N2, which has been characterized by X-ray diffraction. The solid-state structure established a distorted octahedral geometry where the hydride ligand distorts toward the iron silyl. Both (iPrPNP)FeH2(N2) and (iPrPNP)FeH(SiH2Ph)N2 form η2-dihydrogen complexes upon exposure to H2. The iron hydrides and the η2-H2 ligands are in rapid exchange in solution, consistent with the previously reported "cis" effect, arising from a dipole/induced dipole interaction between the two ligands. Taken together, the spectroscopic, structural, and reactivity studies highlight the relative electron-donating ability of this pincer ligand as compared to the redox-active aryl-substituted bis(imino)pyridines.
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U2 - 10.1021/ic0608647
DO - 10.1021/ic0608647
M3 - Article
VL - 45
SP - 7252
EP - 7260
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 18
ER -