Low-Valent Iron Mono-Diazadiene Compounds: Electronic Structure and Catalytic Application

Crispin Lichtenberg; Mario Adelhardt; Thomas L. Gianetti; Karsten Meyer; Bas De Bruin; Hansjörg Grützmacher

doi:10.1021/acscatal.5b01416

Low-Valent Iron Mono-Diazadiene Compounds: Electronic Structure and Catalytic Application

Crispin Lichtenberg, Mario Adelhardt, Thomas L. Gianetti, Karsten Meyer, Bas De Bruin, Hansjörg Grützmacher

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

48 Scopus citations

Abstract

A series of monodiazadiene diolefin iron compounds, [Fe(trop₂dad)(L)] (4; L = neutral ligand), has been prepared by one-electron oxidation of the Fe^I species [NaFe(trop₂dad)(thf)₃] (dad = diazadiene; trop = 5H-dibenzo[a,d]cyclohepten-5-yl). The electronic structures of compounds 4 were investigated by NMR and Mössbauer spectroscopy, single-crystal X-ray diffraction, solid- and liquid-phase magnetic susceptibility measurements, and DFT calculations. Compounds of type 4 with labile ligands L were found to be active (pre)catalysts for the dehydrogenative coupling of (alkyl)amine-boranes. Remarkably high activities were observed, especially for the homogeneous dehydrogenative polymerization of methylamine-borane.

Original language	English (US)
Pages (from-to)	6230-6240
Number of pages	11
Journal	ACS Catalysis
Volume	5
Issue number	10
DOIs	https://doi.org/10.1021/acscatal.5b01416
State	Published - Oct 2 2015
Externally published	Yes

Keywords

dehydrogenative polymerization
electronic structure determination
homogeneous catalysis
iron diazadiene compounds
methylamine-borane

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1021/acscatal.5b01416

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title = "Low-Valent Iron Mono-Diazadiene Compounds: Electronic Structure and Catalytic Application",

abstract = "A series of monodiazadiene diolefin iron compounds, [Fe(trop2dad)(L)] (4; L = neutral ligand), has been prepared by one-electron oxidation of the FeI species [NaFe(trop2dad)(thf)3] (dad = diazadiene; trop = 5H-dibenzo[a,d]cyclohepten-5-yl). The electronic structures of compounds 4 were investigated by NMR and M{\"o}ssbauer spectroscopy, single-crystal X-ray diffraction, solid- and liquid-phase magnetic susceptibility measurements, and DFT calculations. Compounds of type 4 with labile ligands L were found to be active (pre)catalysts for the dehydrogenative coupling of (alkyl)amine-boranes. Remarkably high activities were observed, especially for the homogeneous dehydrogenative polymerization of methylamine-borane.",

keywords = "dehydrogenative polymerization, electronic structure determination, homogeneous catalysis, iron diazadiene compounds, methylamine-borane",

author = "Crispin Lichtenberg and Mario Adelhardt and Gianetti, {Thomas L.} and Karsten Meyer and {De Bruin}, Bas and Hansj{\"o}rg Gr{\"u}tzmacher",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2015",

month = oct,

day = "2",

doi = "10.1021/acscatal.5b01416",

language = "English (US)",

volume = "5",

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journal = "ACS Catalysis",

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T1 - Low-Valent Iron Mono-Diazadiene Compounds

T2 - Electronic Structure and Catalytic Application

AU - Lichtenberg, Crispin

AU - Adelhardt, Mario

AU - Gianetti, Thomas L.

AU - Meyer, Karsten

AU - De Bruin, Bas

AU - Grützmacher, Hansjörg

PY - 2015/10/2

Y1 - 2015/10/2

N2 - A series of monodiazadiene diolefin iron compounds, [Fe(trop2dad)(L)] (4; L = neutral ligand), has been prepared by one-electron oxidation of the FeI species [NaFe(trop2dad)(thf)3] (dad = diazadiene; trop = 5H-dibenzo[a,d]cyclohepten-5-yl). The electronic structures of compounds 4 were investigated by NMR and Mössbauer spectroscopy, single-crystal X-ray diffraction, solid- and liquid-phase magnetic susceptibility measurements, and DFT calculations. Compounds of type 4 with labile ligands L were found to be active (pre)catalysts for the dehydrogenative coupling of (alkyl)amine-boranes. Remarkably high activities were observed, especially for the homogeneous dehydrogenative polymerization of methylamine-borane.

AB - A series of monodiazadiene diolefin iron compounds, [Fe(trop2dad)(L)] (4; L = neutral ligand), has been prepared by one-electron oxidation of the FeI species [NaFe(trop2dad)(thf)3] (dad = diazadiene; trop = 5H-dibenzo[a,d]cyclohepten-5-yl). The electronic structures of compounds 4 were investigated by NMR and Mössbauer spectroscopy, single-crystal X-ray diffraction, solid- and liquid-phase magnetic susceptibility measurements, and DFT calculations. Compounds of type 4 with labile ligands L were found to be active (pre)catalysts for the dehydrogenative coupling of (alkyl)amine-boranes. Remarkably high activities were observed, especially for the homogeneous dehydrogenative polymerization of methylamine-borane.

KW - dehydrogenative polymerization

KW - electronic structure determination

KW - homogeneous catalysis

KW - iron diazadiene compounds

KW - methylamine-borane

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JO - ACS Catalysis

JF - ACS Catalysis

IS - 10

ER -

Low-Valent Iron Mono-Diazadiene Compounds: Electronic Structure and Catalytic Application

Abstract

Keywords

ASJC Scopus subject areas

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