Synthesis of bis(imino)pyridine iron di- And monoalkyl complexes

Stability differences between FeCH2SiMe3 and FeCH 2CMe3 derivatives

Ignacio Fernández, Ryan Trovitch, Emil Lobkovsky, Paul J. Chirik

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

The scope of aryl-substituted bis(imino)pyridine iron dihalide alkylation and arylation reactions has been explored with LiCH2SiMe3, LiCH2CMe3, and LiPh. Dialkylation was only observed when the 2,6-diisopropylaryl-substituted iron complex was treated with 2 equiv of LiCH2SiMe3. In all other cases, reductive alkylation to form four-coordinate bis(imino)pyridine iron monoalkyl complexes occurred. One of these products, (EtPDI)FeCH2CMe3 [ EtPDI = 2,6-(2,6-Et2C6H3N=CMe) 2C6H3N)], has been crystallographically characterized and shown to exhibit a distorted square planar geometry arising from the steric disposition of the alkyl group. Five-coordinate bis(imino)pyridine iron aryl"ate" complexes bearing weakly activated dinitrogen ligands were isolated from treatment of the corresponding dihalide with 3 equiv of aryllithium. The tolyl derivative was characterized by X-ray diffraction, and a distorted square pyramidal structure was established where the dinitrogen ligand completes the idealized basal plane. Ligand substitution reactions where the terdentate bis(imino)pyridine is used to displace pyridine from Py2Fe(R)X (R = CH2SiMe3, CH 2CMe3; X = Cl, CH2SiMe3, CH 2CMe3) further demonstrated the relative stability of five-coordinate FeCH2SiMe3 versus FeCH2CMe 3 complexes. For the neopentyl compounds, ejection of a neopentyl radical or alkylation of the p-pyridine position of the chelate was observed.

Original languageEnglish
Pages (from-to)109-118
Number of pages10
JournalOrganometallics
Volume27
Issue number1
DOIs
Publication statusPublished - Jan 14 2008

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pyridines
Iron
Derivatives
iron
alkylation
Alkylation
synthesis
Ligands
ligands
Bearings (structural)
methylidyne
chelates
ejection
pyridine
Substitution reactions
substitutes
X ray diffraction
Geometry
products
geometry

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Synthesis of bis(imino)pyridine iron di- And monoalkyl complexes : Stability differences between FeCH2SiMe3 and FeCH 2CMe3 derivatives. / Fernández, Ignacio; Trovitch, Ryan; Lobkovsky, Emil; Chirik, Paul J.

In: Organometallics, Vol. 27, No. 1, 14.01.2008, p. 109-118.

Research output: Contribution to journalArticle

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abstract = "The scope of aryl-substituted bis(imino)pyridine iron dihalide alkylation and arylation reactions has been explored with LiCH2SiMe3, LiCH2CMe3, and LiPh. Dialkylation was only observed when the 2,6-diisopropylaryl-substituted iron complex was treated with 2 equiv of LiCH2SiMe3. In all other cases, reductive alkylation to form four-coordinate bis(imino)pyridine iron monoalkyl complexes occurred. One of these products, (EtPDI)FeCH2CMe3 [ EtPDI = 2,6-(2,6-Et2C6H3N=CMe) 2C6H3N)], has been crystallographically characterized and shown to exhibit a distorted square planar geometry arising from the steric disposition of the alkyl group. Five-coordinate bis(imino)pyridine iron aryl{"}ate{"} complexes bearing weakly activated dinitrogen ligands were isolated from treatment of the corresponding dihalide with 3 equiv of aryllithium. The tolyl derivative was characterized by X-ray diffraction, and a distorted square pyramidal structure was established where the dinitrogen ligand completes the idealized basal plane. Ligand substitution reactions where the terdentate bis(imino)pyridine is used to displace pyridine from Py2Fe(R)X (R = CH2SiMe3, CH 2CMe3; X = Cl, CH2SiMe3, CH 2CMe3) further demonstrated the relative stability of five-coordinate FeCH2SiMe3 versus FeCH2CMe 3 complexes. For the neopentyl compounds, ejection of a neopentyl radical or alkylation of the p-pyridine position of the chelate was observed.",
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AB - The scope of aryl-substituted bis(imino)pyridine iron dihalide alkylation and arylation reactions has been explored with LiCH2SiMe3, LiCH2CMe3, and LiPh. Dialkylation was only observed when the 2,6-diisopropylaryl-substituted iron complex was treated with 2 equiv of LiCH2SiMe3. In all other cases, reductive alkylation to form four-coordinate bis(imino)pyridine iron monoalkyl complexes occurred. One of these products, (EtPDI)FeCH2CMe3 [ EtPDI = 2,6-(2,6-Et2C6H3N=CMe) 2C6H3N)], has been crystallographically characterized and shown to exhibit a distorted square planar geometry arising from the steric disposition of the alkyl group. Five-coordinate bis(imino)pyridine iron aryl"ate" complexes bearing weakly activated dinitrogen ligands were isolated from treatment of the corresponding dihalide with 3 equiv of aryllithium. The tolyl derivative was characterized by X-ray diffraction, and a distorted square pyramidal structure was established where the dinitrogen ligand completes the idealized basal plane. Ligand substitution reactions where the terdentate bis(imino)pyridine is used to displace pyridine from Py2Fe(R)X (R = CH2SiMe3, CH 2CMe3; X = Cl, CH2SiMe3, CH 2CMe3) further demonstrated the relative stability of five-coordinate FeCH2SiMe3 versus FeCH2CMe 3 complexes. For the neopentyl compounds, ejection of a neopentyl radical or alkylation of the p-pyridine position of the chelate was observed.

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