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

Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.

doi:10.1021/acs.organomet.6b00108

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

Journal Article · Mon May 23 00:00:00 EDT 2016 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.6b00108· OSTI ID:1352415

Tondreau, Aaron M. ^[1]; Scott, Brian L. ^[1]; Boncella, James M. ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Chemistry and MPA Divisions

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.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1352415

Report Number(s):: LA-UR-15-29082

Journal Information:: Organometallics, Vol. 35, Issue 11; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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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

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