Reactivity of Complexes of 4fn5d1 and 4fn+1 Ln2+ Ions with Cyclooctatetraene

Chad T. Palumbo; Megan E. Fieser; Joseph W. Ziller; William J. Evans

doi:10.1021/acs.organomet.7b00498

Reactivity of Complexes of 4fⁿ5d¹ and 4fⁿ⁺¹ Ln²⁺ Ions with Cyclooctatetraene

Chad T. Palumbo, Megan E. Fieser, Joseph W. Ziller, William J. Evans

Chemistry (Twin Cities)

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

13 Scopus citations

Abstract

The Ln²⁺ complexes [K(2.2.2-cryptand)][Cp′₃Ln] (Ln = La, Ce, Pr, Nd, Sm, Eu, Dy, Tm, Yb; Cp′ = C₅H₄SiMe₃) were reacted with 1,3,5,7-cyclooctatetraene, C₈H₈, to determine if the reactivity of the complexes of 4fⁿ⁺¹ ions differed from that of 4fⁿ5d¹ ions. Crystallographically characterizable (C₈H₈)^2- complexes were obtained only for the larger metals in the lanthanide series, and two types of products were obtained: [K(2.2.2-cryptand)][Cp′₂Ln(C₈H₈)] (Ln = La, Ce) and [K(2.2.2-cryptand)][Ln(C₈H₈)₂] (Ln = Ce, Pr, Nd, Sm). The expected co-products of the two-electron reduction of C₈H₈ by 2 equiv of [K(2.2.2-cryptand)][Cp′₃Ln], namely, the tetrakis(cyclopentadienyl) complexes, [K(2.2.2-cryptand)][Cp′₄Ln], were crystallographically characterized for six metals (Ln = Ce, Pr, Nd, Sm, Dy, Tm).

Original language	English (US)
Pages (from-to)	3721-3728
Number of pages	8
Journal	Organometallics
Volume	36
Issue number	19
DOIs	https://doi.org/10.1021/acs.organomet.7b00498
State	Published - Oct 9 2017

Bibliographical note

Funding Information:
This research was supported by the National Science Foundation (NSF) under CHE-1565776 to W.J.E. We thank Dr. Jordan F. Corbey and Dr. Jason R. Jones for crystallographic assistance. We also thank NSF for providing graduate fellowship support for C.T.P. (DGE-1321846).

Publisher Copyright:
© 2017 American Chemical Society.

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10.1021/acs.organomet.7b00498

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@article{e83f5ff6d73a4f2faa62a1e68ec1387d,

title = "Reactivity of Complexes of 4fn5d1 and 4fn+1 Ln2+ Ions with Cyclooctatetraene",

abstract = "The Ln2+ complexes [K(2.2.2-cryptand)][Cp′3Ln] (Ln = La, Ce, Pr, Nd, Sm, Eu, Dy, Tm, Yb; Cp′ = C5H4SiMe3) were reacted with 1,3,5,7-cyclooctatetraene, C8H8, to determine if the reactivity of the complexes of 4fn+1 ions differed from that of 4fn5d1 ions. Crystallographically characterizable (C8H8)2- complexes were obtained only for the larger metals in the lanthanide series, and two types of products were obtained: [K(2.2.2-cryptand)][Cp′2Ln(C8H8)] (Ln = La, Ce) and [K(2.2.2-cryptand)][Ln(C8H8)2] (Ln = Ce, Pr, Nd, Sm). The expected co-products of the two-electron reduction of C8H8 by 2 equiv of [K(2.2.2-cryptand)][Cp′3Ln], namely, the tetrakis(cyclopentadienyl) complexes, [K(2.2.2-cryptand)][Cp′4Ln], were crystallographically characterized for six metals (Ln = Ce, Pr, Nd, Sm, Dy, Tm).",

author = "Palumbo, {Chad T.} and Fieser, {Megan E.} and Ziller, {Joseph W.} and Evans, {William J.}",

note = "Funding Information: This research was supported by the National Science Foundation (NSF) under CHE-1565776 to W.J.E. We thank Dr. Jordan F. Corbey and Dr. Jason R. Jones for crystallographic assistance. We also thank NSF for providing graduate fellowship support for C.T.P. (DGE-1321846). Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

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doi = "10.1021/acs.organomet.7b00498",

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T1 - Reactivity of Complexes of 4fn5d1 and 4fn+1 Ln2+ Ions with Cyclooctatetraene

AU - Palumbo, Chad T.

AU - Fieser, Megan E.

AU - Ziller, Joseph W.

AU - Evans, William J.

N1 - Funding Information: This research was supported by the National Science Foundation (NSF) under CHE-1565776 to W.J.E. We thank Dr. Jordan F. Corbey and Dr. Jason R. Jones for crystallographic assistance. We also thank NSF for providing graduate fellowship support for C.T.P. (DGE-1321846). Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/10/9

Y1 - 2017/10/9

N2 - The Ln2+ complexes [K(2.2.2-cryptand)][Cp′3Ln] (Ln = La, Ce, Pr, Nd, Sm, Eu, Dy, Tm, Yb; Cp′ = C5H4SiMe3) were reacted with 1,3,5,7-cyclooctatetraene, C8H8, to determine if the reactivity of the complexes of 4fn+1 ions differed from that of 4fn5d1 ions. Crystallographically characterizable (C8H8)2- complexes were obtained only for the larger metals in the lanthanide series, and two types of products were obtained: [K(2.2.2-cryptand)][Cp′2Ln(C8H8)] (Ln = La, Ce) and [K(2.2.2-cryptand)][Ln(C8H8)2] (Ln = Ce, Pr, Nd, Sm). The expected co-products of the two-electron reduction of C8H8 by 2 equiv of [K(2.2.2-cryptand)][Cp′3Ln], namely, the tetrakis(cyclopentadienyl) complexes, [K(2.2.2-cryptand)][Cp′4Ln], were crystallographically characterized for six metals (Ln = Ce, Pr, Nd, Sm, Dy, Tm).

AB - The Ln2+ complexes [K(2.2.2-cryptand)][Cp′3Ln] (Ln = La, Ce, Pr, Nd, Sm, Eu, Dy, Tm, Yb; Cp′ = C5H4SiMe3) were reacted with 1,3,5,7-cyclooctatetraene, C8H8, to determine if the reactivity of the complexes of 4fn+1 ions differed from that of 4fn5d1 ions. Crystallographically characterizable (C8H8)2- complexes were obtained only for the larger metals in the lanthanide series, and two types of products were obtained: [K(2.2.2-cryptand)][Cp′2Ln(C8H8)] (Ln = La, Ce) and [K(2.2.2-cryptand)][Ln(C8H8)2] (Ln = Ce, Pr, Nd, Sm). The expected co-products of the two-electron reduction of C8H8 by 2 equiv of [K(2.2.2-cryptand)][Cp′3Ln], namely, the tetrakis(cyclopentadienyl) complexes, [K(2.2.2-cryptand)][Cp′4Ln], were crystallographically characterized for six metals (Ln = Ce, Pr, Nd, Sm, Dy, Tm).

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