Kinetic solvent effects in the reduction of alkyl halides by {Sm[N(SiMe3)2]2(THF)2}

Tesia V. Chciuk; Sandeepan Maity; Robert A. Flowers

doi:10.1016/j.jorganchem.2017.10.018

Kinetic solvent effects in the reduction of alkyl halides by {Sm[N(SiMe₃)₂]₂(THF)₂}

Tesia V. Chciuk, Sandeepan Maity, Robert A. Flowers

Lehigh University

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

The rate of reduction of two representative alkyl halides, 1-bromododecane and 1-chlorododecane by {Sm[N(SiMe₃)₂]₂(THF)₂} was examined in five different solvents. Reductions were several orders of magnitude faster in nonpolar, non-coordinating solvents than in polar coordinating solvents. Good correlations between the rate of reduction and coordination index of each solvent was obtained whereas excellent correlations were obtained between rates and dielectric (as a measure of solvent polarity). The basis of this effect is proposed to be a consequence of solvent coordination to the inner sphere of Sm(II) leading to a deceleration of ET in coordinating solvents and possible transition state stabilization by nonpolar solvents.

Original language	English
Pages (from-to)	52-57
Number of pages	6
Journal	Journal of Organometallic Chemistry
Volume	857
DOIs	https://doi.org/10.1016/j.jorganchem.2017.10.018
State	Published - 15 Feb 2018
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2017 Elsevier B.V.

Funding

R.A.F. is grateful the National Science Foundation ( CHE 1565741 ) for support of this work. We thank Dr. Lawrence Courtney and Dr. Gregory Ferguson in the Department of Chemistry at Lehigh University for insightful discussions.

Funders	Funder number
National Science Foundation	1565741, CHE 1565741

Keywords

Dissociative electron transfer
Inner-sphere
Samarium
Solvation

Access to Document

10.1016/j.jorganchem.2017.10.018

Cite this

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abstract = "The rate of reduction of two representative alkyl halides, 1-bromododecane and 1-chlorododecane by {Sm[N(SiMe3)2]2(THF)2} was examined in five different solvents. Reductions were several orders of magnitude faster in nonpolar, non-coordinating solvents than in polar coordinating solvents. Good correlations between the rate of reduction and coordination index of each solvent was obtained whereas excellent correlations were obtained between rates and dielectric (as a measure of solvent polarity). The basis of this effect is proposed to be a consequence of solvent coordination to the inner sphere of Sm(II) leading to a deceleration of ET in coordinating solvents and possible transition state stabilization by nonpolar solvents.",

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AB - The rate of reduction of two representative alkyl halides, 1-bromododecane and 1-chlorododecane by {Sm[N(SiMe3)2]2(THF)2} was examined in five different solvents. Reductions were several orders of magnitude faster in nonpolar, non-coordinating solvents than in polar coordinating solvents. Good correlations between the rate of reduction and coordination index of each solvent was obtained whereas excellent correlations were obtained between rates and dielectric (as a measure of solvent polarity). The basis of this effect is proposed to be a consequence of solvent coordination to the inner sphere of Sm(II) leading to a deceleration of ET in coordinating solvents and possible transition state stabilization by nonpolar solvents.

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