Bis(diisopropylphosphino)pyridine iron dicarbonyl, dihydride, and silyl hydride complexes

Ryan J. Trovitch; Emil Lobkovsky; Paul J. Chirik

doi:10.1021/ic0608647

Bis(diisopropylphosphino)pyridine iron dicarbonyl, dihydride, and silyl hydride complexes

Ryan J. Trovitch, Emil Lobkovsky, Paul J. Chirik

Research output: Contribution to journal › Article › peer-review

145 Scopus citations

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 (US)
Pages (from-to)	7252-7260
Number of pages	9
Journal	Inorganic chemistry
Volume	45
Issue number	18
DOIs	https://doi.org/10.1021/ic0608647
State	Published - Sep 4 2006
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Bis(diisopropylphosphino)pyridine iron dicarbonyl, dihydride, and silyl hydride complexes",

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.",

author = "Trovitch, {Ryan J.} and Emil Lobkovsky and Chirik, {Paul J.}",

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T1 - Bis(diisopropylphosphino)pyridine iron dicarbonyl, dihydride, and silyl hydride complexes

AU - Trovitch, Ryan J.

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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Bis(diisopropylphosphino)pyridine iron dicarbonyl, dihydride, and silyl hydride complexes

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