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

Ryan Trovitch, Emil Lobkovsky, Paul J. Chirik

Research output: Contribution to journalArticle

123 Citations (Scopus)

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 languageEnglish
Pages (from-to)7252-7260
Number of pages9
JournalInorganic Chemistry
Volume45
Issue number18
DOIs
Publication statusPublished - Sep 4 2006

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dihydrides
Hydrides
hydrides
pyridines
Iron
Ligands
iron
ligands
dipoles
Pyridines
dichlorides
Ion exchange
Substitution reactions
reactivity
substitutes
solid state
atmospheres
X ray diffraction
Geometry
pyridine

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 journalArticle

Trovitch, Ryan ; Lobkovsky, Emil ; Chirik, Paul J. / Bis(diisopropylphosphino)pyridine iron dicarbonyl, dihydride, and silyl hydride complexes. In: Inorganic Chemistry. 2006 ; Vol. 45, No. 18. pp. 7252-7260.
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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.",
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