Preparation and molecular and electronic structures of iron(0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation

Suzanne C. Bart; Emil Lobkovsky; Paul J. Chirik

doi:10.1021/ja046753t

Preparation and molecular and electronic structures of iron(0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation

Suzanne C. Bart, Emil Lobkovsky, Paul J. Chirik

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

710 Scopus citations

Abstract

Reduction of the five-coordinate iron(II) dihalide complexes ( ^iPrPDI)FeX₂ (^iPrPDI = ((2,6-CHMe ₂)₂C₆H₃N=CMe)₂C ₅H₃N; X = Cl, Br) with sodium amalgam under 1 atm of dinitrogen afforded the square pyramidal, high spin iron(0) bis(dinitrogen) complex (^iPrPDI)Fe(N₂)₂. In solution, ( ^iPrPDI)Fe(N₂)₂ loses 1 equiv of N₂ to afford the mono(dinitrogen) adduct (^iPrPDI)Fe(N₂) ₂. Both dinitrogen compounds serve as effective precatalysts for the hydrogenation and hydrosilation of olefins and alkynes. Effecient catalytic reactions are observed with low catalyst loadings (≤0.3 mol %) at ambient temperature in nonpolar media. The catalytic hydrosilations are selective in forming the anti-Markovnikov product. Structural characterization of a high spin iron(0) alkyne and a bis(silane) σ-complex has also been accomplished and in combination with isotopic labeling studies provides insight into the mechanism of both catalytic C-H and catalytic C-Si bond formation.

Original language	English (US)
Pages (from-to)	13794-13807
Number of pages	14
Journal	Journal of the American Chemical Society
Volume	126
Issue number	42
DOIs	https://doi.org/10.1021/ja046753t
State	Published - Oct 27 2004
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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@article{31108d1755b5480c80f3d970f2967283,

title = "Preparation and molecular and electronic structures of iron(0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation",

abstract = "Reduction of the five-coordinate iron(II) dihalide complexes ( iPrPDI)FeX2 (iPrPDI = ((2,6-CHMe 2)2C6H3N=CMe)2C 5H3N; X = Cl, Br) with sodium amalgam under 1 atm of dinitrogen afforded the square pyramidal, high spin iron(0) bis(dinitrogen) complex (iPrPDI)Fe(N2)2. In solution, ( iPrPDI)Fe(N2)2 loses 1 equiv of N2 to afford the mono(dinitrogen) adduct (iPrPDI)Fe(N2) 2. Both dinitrogen compounds serve as effective precatalysts for the hydrogenation and hydrosilation of olefins and alkynes. Effecient catalytic reactions are observed with low catalyst loadings (≤0.3 mol %) at ambient temperature in nonpolar media. The catalytic hydrosilations are selective in forming the anti-Markovnikov product. Structural characterization of a high spin iron(0) alkyne and a bis(silane) σ-complex has also been accomplished and in combination with isotopic labeling studies provides insight into the mechanism of both catalytic C-H and catalytic C-Si bond formation.",

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Preparation and molecular and electronic structures of iron(0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation. / Bart, Suzanne C.; Lobkovsky, Emil; Chirik, Paul J.
In: Journal of the American Chemical Society, Vol. 126, No. 42, 27.10.2004, p. 13794-13807.

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

TY - JOUR

T1 - Preparation and molecular and electronic structures of iron(0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation

AU - Bart, Suzanne C.

AU - Lobkovsky, Emil

AU - Chirik, Paul J.

PY - 2004/10/27

Y1 - 2004/10/27

N2 - Reduction of the five-coordinate iron(II) dihalide complexes ( iPrPDI)FeX2 (iPrPDI = ((2,6-CHMe 2)2C6H3N=CMe)2C 5H3N; X = Cl, Br) with sodium amalgam under 1 atm of dinitrogen afforded the square pyramidal, high spin iron(0) bis(dinitrogen) complex (iPrPDI)Fe(N2)2. In solution, ( iPrPDI)Fe(N2)2 loses 1 equiv of N2 to afford the mono(dinitrogen) adduct (iPrPDI)Fe(N2) 2. Both dinitrogen compounds serve as effective precatalysts for the hydrogenation and hydrosilation of olefins and alkynes. Effecient catalytic reactions are observed with low catalyst loadings (≤0.3 mol %) at ambient temperature in nonpolar media. The catalytic hydrosilations are selective in forming the anti-Markovnikov product. Structural characterization of a high spin iron(0) alkyne and a bis(silane) σ-complex has also been accomplished and in combination with isotopic labeling studies provides insight into the mechanism of both catalytic C-H and catalytic C-Si bond formation.

AB - Reduction of the five-coordinate iron(II) dihalide complexes ( iPrPDI)FeX2 (iPrPDI = ((2,6-CHMe 2)2C6H3N=CMe)2C 5H3N; X = Cl, Br) with sodium amalgam under 1 atm of dinitrogen afforded the square pyramidal, high spin iron(0) bis(dinitrogen) complex (iPrPDI)Fe(N2)2. In solution, ( iPrPDI)Fe(N2)2 loses 1 equiv of N2 to afford the mono(dinitrogen) adduct (iPrPDI)Fe(N2) 2. Both dinitrogen compounds serve as effective precatalysts for the hydrogenation and hydrosilation of olefins and alkynes. Effecient catalytic reactions are observed with low catalyst loadings (≤0.3 mol %) at ambient temperature in nonpolar media. The catalytic hydrosilations are selective in forming the anti-Markovnikov product. Structural characterization of a high spin iron(0) alkyne and a bis(silane) σ-complex has also been accomplished and in combination with isotopic labeling studies provides insight into the mechanism of both catalytic C-H and catalytic C-Si bond formation.

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ER -

Preparation and molecular and electronic structures of iron(0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation

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