Isolation and Characterization of the First σ-Organomanganese(III) Complex. Crystal and Molecular Structure of (2,4,6-Trlmethylphenyl)-dlbromobls(trlmethylphosphlne)manganese(III)

Robert J. Morris; Gregory S. Girolami

doi:10.1021/om00151a035

Isolation and Characterization of the First σ-Organomanganese(III) Complex. Crystal and Molecular Structure of (2,4,6-Trlmethylphenyl)-dlbromobls(trlmethylphosphlne)manganese(III)

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Abstract

Alkylation of MnBr₂with the mesityl (2,4,6-trimethylphenyl) reagent Mg(C₆H₂Me₃)₂(THF)₂in the presence of trimethylphosphine followed by reaction with 1 equiv of oxygen yields dark red crystals of Mn-(C₆H₂Me3)Br₂(PMe3)₂, which is the first isolated example of a σr-organomanganese(III) complex. This high-spin (μ = μ_B)complex adopts a distorted trigonal-bipyramidal structure of approximate C_2vsymmetry with the phosphine ligands occupying the axial sites. The metal-ligand distances are consistent with a trivalent oxidation state, while the orientation of the mesityl ring in the equatorial plane and the interligand angles can be rationalized on steric grounds.

Original language	English (US)
Pages (from-to)	1815-1816
Number of pages	2
Journal	Organometallics
Volume	6
Issue number	8
DOIs	https://doi.org/10.1021/om00151a035
State	Published - Aug 1 1987

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Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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abstract = "Alkylation of MnBr2with the mesityl (2,4,6-trimethylphenyl) reagent Mg(C6H2Me3)2(THF)2in the presence of trimethylphosphine followed by reaction with 1 equiv of oxygen yields dark red crystals of Mn-(C6H2Me3)Br2(PMe3)2, which is the first isolated example of a σr-organomanganese(III) complex. This high-spin (μ = μB)complex adopts a distorted trigonal-bipyramidal structure of approximate C2vsymmetry with the phosphine ligands occupying the axial sites. The metal-ligand distances are consistent with a trivalent oxidation state, while the orientation of the mesityl ring in the equatorial plane and the interligand angles can be rationalized on steric grounds.",

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AU - Girolami, Gregory S.

PY - 1987/8/1

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N2 - Alkylation of MnBr2with the mesityl (2,4,6-trimethylphenyl) reagent Mg(C6H2Me3)2(THF)2in the presence of trimethylphosphine followed by reaction with 1 equiv of oxygen yields dark red crystals of Mn-(C6H2Me3)Br2(PMe3)2, which is the first isolated example of a σr-organomanganese(III) complex. This high-spin (μ = μB)complex adopts a distorted trigonal-bipyramidal structure of approximate C2vsymmetry with the phosphine ligands occupying the axial sites. The metal-ligand distances are consistent with a trivalent oxidation state, while the orientation of the mesityl ring in the equatorial plane and the interligand angles can be rationalized on steric grounds.

AB - Alkylation of MnBr2with the mesityl (2,4,6-trimethylphenyl) reagent Mg(C6H2Me3)2(THF)2in the presence of trimethylphosphine followed by reaction with 1 equiv of oxygen yields dark red crystals of Mn-(C6H2Me3)Br2(PMe3)2, which is the first isolated example of a σr-organomanganese(III) complex. This high-spin (μ = μB)complex adopts a distorted trigonal-bipyramidal structure of approximate C2vsymmetry with the phosphine ligands occupying the axial sites. The metal-ligand distances are consistent with a trivalent oxidation state, while the orientation of the mesityl ring in the equatorial plane and the interligand angles can be rationalized on steric grounds.

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Isolation and Characterization of the First σ-Organomanganese(III) Complex. Crystal and Molecular Structure of (2,4,6-Trlmethylphenyl)-dlbromobls(trlmethylphosphlne)manganese(III)

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