Tetravalent Cerium Alkyl and Benzyl Complexes

Haruko Tateyama; Andrew C. Boggiano; Can Liao; Kaitlyn S. Otte; Xiaosong Li; Henry S. La Pierre

doi:10.1021/jacs.4c01964

Tetravalent Cerium Alkyl and Benzyl Complexes

Haruko Tateyama
, Andrew C. Boggiano
, Can Liao
, Kaitlyn S. Otte
, Xiaosong Li
, Henry S. La Pierre

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

20 Scopus citations

Abstract

High-valent cerium complexes of alkyl and benzyl ligands are unprecedented due to the incompatibility of the typically highly oxidizing Ce⁴⁺ ion and the reducing alkyl or benzyl ligand. Herein we report the synthesis and isolation of the first tetravalent cerium alkyl and benzyl complexes supported by the tri-tert-butyl imidophosphorane ligand, [NP(^tBu)₃]^1-. The Ce⁴⁺ monoiodide complex, [Ce⁴⁺I(NP(tert-butyl)₃)₃] (1-CeI), serves as a precursor to the alkyl and benzyl complexes, [Ce⁴⁺(Npt)(NP(tert-butyl)₃)₃] (2-CeNpt) (Npt = neopentyl, CH₂C(CH₃)₃) and [Ce⁴⁺(Bn)(NP(tert-butyl)₃)₃] (2-CeBn) (Bn = benzyl, CH₂Ph). The bonding and structure of these complexes are characterized by single-crystal XRD, NMR and UV-vis-NIR spectroscopy, cyclic voltammetry, and DFT studies.

Original language	English
Pages (from-to)	10268-10273
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	146
Issue number	15
DOIs	https://doi.org/10.1021/jacs.4c01964
State	Published - Apr 17 2024
Externally published	Yes

Funding

This material is based upon work supported by the National Science Foundation (NSF) through the Faculty Career Development Program (CAREER) under award No. 1943452 (HT, ACB, HSL). Studies of lanthanide electronic structure are supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under the Quantum Information Science initiative, Grant No. DE-SC0023455 (CL, XSL). Single-crystal diffraction experiments were conducted at the GT-XRD facility.

Access to Document

10.1021/jacs.4c01964

Cite this

@article{0f6fd33d88e24204a4982add73ec6e67,

title = "Tetravalent Cerium Alkyl and Benzyl Complexes",

abstract = "High-valent cerium complexes of alkyl and benzyl ligands are unprecedented due to the incompatibility of the typically highly oxidizing Ce4+ ion and the reducing alkyl or benzyl ligand. Herein we report the synthesis and isolation of the first tetravalent cerium alkyl and benzyl complexes supported by the tri-tert-butyl imidophosphorane ligand, [NP(tBu)3]1-. The Ce4+ monoiodide complex, [Ce4+I(NP(tert-butyl)3)3] (1-CeI), serves as a precursor to the alkyl and benzyl complexes, [Ce4+(Npt)(NP(tert-butyl)3)3] (2-CeNpt) (Npt = neopentyl, CH2C(CH3)3) and [Ce4+(Bn)(NP(tert-butyl)3)3] (2-CeBn) (Bn = benzyl, CH2Ph). The bonding and structure of these complexes are characterized by single-crystal XRD, NMR and UV-vis-NIR spectroscopy, cyclic voltammetry, and DFT studies.",

author = "Haruko Tateyama and Boggiano, \{Andrew C.\} and Can Liao and Otte, \{Kaitlyn S.\} and Xiaosong Li and \{La Pierre\}, \{Henry S.\}",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society.",

year = "2024",

month = apr,

day = "17",

doi = "10.1021/jacs.4c01964",

language = "English",

volume = "146",

pages = "10268--10273",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "15",

}

TY - JOUR

T1 - Tetravalent Cerium Alkyl and Benzyl Complexes

AU - Tateyama, Haruko

AU - Boggiano, Andrew C.

AU - Liao, Can

AU - Otte, Kaitlyn S.

AU - Li, Xiaosong

AU - La Pierre, Henry S.

PY - 2024/4/17

Y1 - 2024/4/17

N2 - High-valent cerium complexes of alkyl and benzyl ligands are unprecedented due to the incompatibility of the typically highly oxidizing Ce4+ ion and the reducing alkyl or benzyl ligand. Herein we report the synthesis and isolation of the first tetravalent cerium alkyl and benzyl complexes supported by the tri-tert-butyl imidophosphorane ligand, [NP(tBu)3]1-. The Ce4+ monoiodide complex, [Ce4+I(NP(tert-butyl)3)3] (1-CeI), serves as a precursor to the alkyl and benzyl complexes, [Ce4+(Npt)(NP(tert-butyl)3)3] (2-CeNpt) (Npt = neopentyl, CH2C(CH3)3) and [Ce4+(Bn)(NP(tert-butyl)3)3] (2-CeBn) (Bn = benzyl, CH2Ph). The bonding and structure of these complexes are characterized by single-crystal XRD, NMR and UV-vis-NIR spectroscopy, cyclic voltammetry, and DFT studies.

AB - High-valent cerium complexes of alkyl and benzyl ligands are unprecedented due to the incompatibility of the typically highly oxidizing Ce4+ ion and the reducing alkyl or benzyl ligand. Herein we report the synthesis and isolation of the first tetravalent cerium alkyl and benzyl complexes supported by the tri-tert-butyl imidophosphorane ligand, [NP(tBu)3]1-. The Ce4+ monoiodide complex, [Ce4+I(NP(tert-butyl)3)3] (1-CeI), serves as a precursor to the alkyl and benzyl complexes, [Ce4+(Npt)(NP(tert-butyl)3)3] (2-CeNpt) (Npt = neopentyl, CH2C(CH3)3) and [Ce4+(Bn)(NP(tert-butyl)3)3] (2-CeBn) (Bn = benzyl, CH2Ph). The bonding and structure of these complexes are characterized by single-crystal XRD, NMR and UV-vis-NIR spectroscopy, cyclic voltammetry, and DFT studies.

UR - https://www.scopus.com/pages/publications/85189510394

U2 - 10.1021/jacs.4c01964

DO - 10.1021/jacs.4c01964

M3 - Article

C2 - 38564671

AN - SCOPUS:85189510394

SN - 0002-7863

VL - 146

SP - 10268

EP - 10273

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 15

ER -

Tetravalent Cerium Alkyl and Benzyl Complexes

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this