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Title: A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron

Abstract

We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py)4FeCl2. Furthermore, we prepared a series of monoalkylated salts of the type (py)2FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py)4FeCl2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane that readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py)2FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe)2FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe)2FeCl2 gave the reduced Fe(0) nitrogen complex (dmpe)2Fe(N2). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.

Authors:
 [1];  [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Chemistry and MPA Divisions
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1352415
Report Number(s):
LA-UR-15-29082
Journal ID: ISSN 0276-7333
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 35; Journal Issue: 11; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Tondreau, Aaron M., Scott, Brian L., and Boncella, James M. A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron. United States: N. p., 2016. Web. doi:10.1021/acs.organomet.6b00108.
Tondreau, Aaron M., Scott, Brian L., & Boncella, James M. A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron. United States. doi:10.1021/acs.organomet.6b00108.
Tondreau, Aaron M., Scott, Brian L., and Boncella, James M. Mon . "A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron". United States. doi:10.1021/acs.organomet.6b00108. https://www.osti.gov/servlets/purl/1352415.
@article{osti_1352415,
title = {A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron},
author = {Tondreau, Aaron M. and Scott, Brian L. and Boncella, James M.},
abstractNote = {We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py)4FeCl2. Furthermore, we prepared a series of monoalkylated salts of the type (py)2FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py)4FeCl2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane that readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py)2FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe)2FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe)2FeCl2 gave the reduced Fe(0) nitrogen complex (dmpe)2Fe(N2). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.},
doi = {10.1021/acs.organomet.6b00108},
journal = {Organometallics},
number = 11,
volume = 35,
place = {United States},
year = {2016},
month = {5}
}

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Works referencing / citing this record:

CCDC 1496020: Experimental Crystal Structure Determination: ARIQEZ : chloro-bis(ethene-1,2-diylbis(diphenylphosphine))-iron diethyl ether solvate
dataset, July 2016


CCDC 1496022: Experimental Crystal Structure Determination: ARIQOJ : bis(4-(phenyl(trimethylsilyl)methylidene)cyclohexa-2,5-dien-1-ido)-iron
dataset, July 2016


CCDC 1496023: Experimental Crystal Structure Determination: AKEJAD01 : (μ-dinitrogen)-tetrakis(ethane-1,2-diylbis(dimethylphosphine))-di-iron
dataset, July 2016


CCDC 1496024: Experimental Crystal Structure Determination: ARIRAW : chloro-(diphenyl(trimethylsilyl)methyl)-bis(pyridine)-iron(ii) fluorobenzene solvate
dataset, July 2016


CCDC 1496026: Experimental Crystal Structure Determination: (phenyl(phenyl)(trimethylsilyl)methyl)-tris(tetrahydrofuran)-sodium
dataset, July 2016

  • Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.
  • The Cambridge Structural Database (CSD), vp
  • DOI: 10.5517/ccdc.csd.cc1m6qxg

Selective hydrosiloxane synthesis via dehydrogenative coupling of silanols with hydrosilanes catalysed by Fe complexes bearing a tetradentate PNNP ligand
journal, January 2018

  • Takeshita, Tomohiro; Sato, Kazuhiko; Nakajima, Yumiko
  • Dalton Transactions, Vol. 47, Issue 47
  • DOI: 10.1039/c8dt04168g

Selective hydrosiloxane synthesis via dehydrogenative coupling of silanols with hydrosilanes catalysed by Fe complexes bearing a tetradentate PNNP ligand
journal, January 2018

  • Takeshita, Tomohiro; Sato, Kazuhiko; Nakajima, Yumiko
  • Dalton Transactions, Vol. 47, Issue 47
  • DOI: 10.1039/c8dt04168g