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

18 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

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© 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 = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = oct,

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

language = "English (US)",

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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.

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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