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

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

Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853

Organometallics, 2004, 23 (2), pp 237–246

DOI: 10.1021/om034188h

Publication Date (Web): December 19, 2003

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

Abstract

Synthesis and characterization of new, four-coordinate, high-spin iron(II) and manganese(II) complexes of the general form L₂MR₂ (L₂ = neutral chelating ligand, R = alkyl) are described. Alkylation of the α-diimine complex, [ArNC(Me)−C(Me)NAr]FeCl₂ (Ar = 2,6-diisopropylphenyl), as well as the enantiopure iron dichloride compounds, (−)-(sparteine)FeCl₂ and (S)-(^tBuBox)FeCl₂ ((S)-(^tBuBox) = 2,2-bis[2-[4(S)-(R‘)-1,3-oxazolinyl]propane), with LiCH₂SiMe₃ 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(CH₂CMe₃)₂, (−)-(sparteine)Fe(CH₂C₆H₅)₂, and (S)-(^tBuBox)Fe(CH₂C₆H₅)₂ were also prepared and characterized by NMR spectroscopy and elemental analysis. An enantiopure, high-spin, tetrahedral manganese(II) dialkyl complex, (−)-(sparteine)Mn(CH₂SiMe₃)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(C₆F₅)₃ have been examined.

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Published In Issue January 19, 2004
Received September 23, 2003

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Article

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

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Preparation and Molecular and Electronic Structures of Iron(0) Dinitrogen and Silane Complexes and Their Application to Catalytic Hydrogenation and Hydrosilation

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