Synthesis, Reactivity, and Solid State Structures of Four-Coordinate Iron(II) and Manganese(II) Alkyl Complexes

Suzanne C. Bart; Eric J. Hawrelak; Amanda K. Schmisseur; Emil Lobkovsky; Paul J. Chirik

doi:10.1021/om034188h

Synthesis, Reactivity, and Solid State Structures of Four-Coordinate Iron(II) and Manganese(II) Alkyl Complexes

Suzanne C. Bart, Eric J. Hawrelak, Amanda K. Schmisseur, Emil Lobkovsky, Paul J. Chirik

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Abstract

Synthesis and characterization of new, four-coordinate, high-spin iron(II) and manganese(II) complexes of the general form L ₂MR ₂ (L ₂ = neutral chelating ligand, R = alkyl) are described. Alkylation of the α-diimine complex, [ArN=C(Me)-C(Me)=NAr]FeCl ₂ (Ar = 2,6-diisopropylphenyl), as well as the enantiopure iron dichloride compounds, (-)-(sparteine)FeCl ₂ and (S)-( ^tBuBox)FeCl ₂ ((S)-( ^tBuBox) = 2,2-bis[2-[4(S)-(R′)-1,3-oxazolinyl]propane), with LiCH ₂SiMe ₃ afforded the corresponding dialkyl derivatives. Solution magnetic susceptibility measurements and X-ray diffraction studies reveal each of the new iron(II) bis-trimethylsilylmethyl complexes to be high-spin, S = 2, tetrahedral molecules. In addition (-)-(sparteine)Fe(CH ₂CMe ₃) ₂, (-)-(sparteine)Fe(CH ₂C ₆H ₅) ₂, and (S)-( ^tBuBox)Fe(CH ₂C ₆H ₅) ₂ were also prepared and characterized by NMR spectroscopy and elemental analysis. An enantiopure, high-spin, tetrahedral manganese(II) dialkyl complex, (-)-(sparteine)Mn(CH ₂SiMe ₃) ₂, has also been synthesized. The catalytic activity of the new iron complexes in carbon-carbon bond forming processes has been evaluated, and stoichiometric reactions of the dialkyls with olefins, carbon monoxide, and the Lewis acid B(C ₆F ₅) ₃ have been examined.

Original language	English (US)
Pages (from-to)	237-246
Number of pages	10
Journal	Organometallics
Volume	23
Issue number	2
DOIs	https://doi.org/10.1021/om034188h
State	Published - Jan 19 2004
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om034188h

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@article{875cb35cc6e0481db730eddaf9391ead,

title = "Synthesis, Reactivity, and Solid State Structures of Four-Coordinate Iron(II) and Manganese(II) Alkyl Complexes",

abstract = "Synthesis and characterization of new, four-coordinate, high-spin iron(II) and manganese(II) complexes of the general form L 2MR 2 (L 2 = neutral chelating ligand, R = alkyl) are described. Alkylation of the α-diimine complex, [ArN=C(Me)-C(Me)=NAr]FeCl 2 (Ar = 2,6-diisopropylphenyl), as well as the enantiopure iron dichloride compounds, (-)-(sparteine)FeCl 2 and (S)-( tBuBox)FeCl 2 ((S)-( tBuBox) = 2,2-bis[2-[4(S)-(R′)-1,3-oxazolinyl]propane), with LiCH 2SiMe 3 afforded the corresponding dialkyl derivatives. Solution magnetic susceptibility measurements and X-ray diffraction studies reveal each of the new iron(II) bis-trimethylsilylmethyl complexes to be high-spin, S = 2, tetrahedral molecules. In addition (-)-(sparteine)Fe(CH 2CMe 3) 2, (-)-(sparteine)Fe(CH 2C 6H 5) 2, and (S)-( tBuBox)Fe(CH 2C 6H 5) 2 were also prepared and characterized by NMR spectroscopy and elemental analysis. An enantiopure, high-spin, tetrahedral manganese(II) dialkyl complex, (-)-(sparteine)Mn(CH 2SiMe 3) 2, has also been synthesized. The catalytic activity of the new iron complexes in carbon-carbon bond forming processes has been evaluated, and stoichiometric reactions of the dialkyls with olefins, carbon monoxide, and the Lewis acid B(C 6F 5) 3 have been examined.",

author = "Bart, {Suzanne C.} and Hawrelak, {Eric J.} and Schmisseur, {Amanda K.} and Emil Lobkovsky and Chirik, {Paul J.}",

year = "2004",

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doi = "10.1021/om034188h",

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T1 - Synthesis, Reactivity, and Solid State Structures of Four-Coordinate Iron(II) and Manganese(II) Alkyl Complexes

AU - Bart, Suzanne C.

AU - Hawrelak, Eric J.

AU - Schmisseur, Amanda K.

AU - Lobkovsky, Emil

AU - Chirik, Paul J.

PY - 2004/1/19

Y1 - 2004/1/19

N2 - Synthesis and characterization of new, four-coordinate, high-spin iron(II) and manganese(II) complexes of the general form L 2MR 2 (L 2 = neutral chelating ligand, R = alkyl) are described. Alkylation of the α-diimine complex, [ArN=C(Me)-C(Me)=NAr]FeCl 2 (Ar = 2,6-diisopropylphenyl), as well as the enantiopure iron dichloride compounds, (-)-(sparteine)FeCl 2 and (S)-( tBuBox)FeCl 2 ((S)-( tBuBox) = 2,2-bis[2-[4(S)-(R′)-1,3-oxazolinyl]propane), with LiCH 2SiMe 3 afforded the corresponding dialkyl derivatives. Solution magnetic susceptibility measurements and X-ray diffraction studies reveal each of the new iron(II) bis-trimethylsilylmethyl complexes to be high-spin, S = 2, tetrahedral molecules. In addition (-)-(sparteine)Fe(CH 2CMe 3) 2, (-)-(sparteine)Fe(CH 2C 6H 5) 2, and (S)-( tBuBox)Fe(CH 2C 6H 5) 2 were also prepared and characterized by NMR spectroscopy and elemental analysis. An enantiopure, high-spin, tetrahedral manganese(II) dialkyl complex, (-)-(sparteine)Mn(CH 2SiMe 3) 2, has also been synthesized. The catalytic activity of the new iron complexes in carbon-carbon bond forming processes has been evaluated, and stoichiometric reactions of the dialkyls with olefins, carbon monoxide, and the Lewis acid B(C 6F 5) 3 have been examined.

AB - Synthesis and characterization of new, four-coordinate, high-spin iron(II) and manganese(II) complexes of the general form L 2MR 2 (L 2 = neutral chelating ligand, R = alkyl) are described. Alkylation of the α-diimine complex, [ArN=C(Me)-C(Me)=NAr]FeCl 2 (Ar = 2,6-diisopropylphenyl), as well as the enantiopure iron dichloride compounds, (-)-(sparteine)FeCl 2 and (S)-( tBuBox)FeCl 2 ((S)-( tBuBox) = 2,2-bis[2-[4(S)-(R′)-1,3-oxazolinyl]propane), with LiCH 2SiMe 3 afforded the corresponding dialkyl derivatives. Solution magnetic susceptibility measurements and X-ray diffraction studies reveal each of the new iron(II) bis-trimethylsilylmethyl complexes to be high-spin, S = 2, tetrahedral molecules. In addition (-)-(sparteine)Fe(CH 2CMe 3) 2, (-)-(sparteine)Fe(CH 2C 6H 5) 2, and (S)-( tBuBox)Fe(CH 2C 6H 5) 2 were also prepared and characterized by NMR spectroscopy and elemental analysis. An enantiopure, high-spin, tetrahedral manganese(II) dialkyl complex, (-)-(sparteine)Mn(CH 2SiMe 3) 2, has also been synthesized. The catalytic activity of the new iron complexes in carbon-carbon bond forming processes has been evaluated, and stoichiometric reactions of the dialkyls with olefins, carbon monoxide, and the Lewis acid B(C 6F 5) 3 have been examined.

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U2 - 10.1021/om034188h

DO - 10.1021/om034188h

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SN - 0276-7333

VL - 23

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JO - Organometallics

JF - Organometallics

IS - 2

ER -

Synthesis, Reactivity, and Solid State Structures of Four-Coordinate Iron(II) and Manganese(II) Alkyl Complexes

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