Efficient Synthesis, Redox Characteristics, and Electronic Structure of a Tetravalent Tris(cyclopentadienyl)cerium Alkoxide Complex

Antonino Gulino; Maurizio Casarin; Vincent P. Conticello; John G. Gaudiello; Heiko Mauermann; Ignazio Fragalá; Tobin J. Marks

doi:10.1021/om00101a016

Efficient Synthesis, Redox Characteristics, and Electronic Structure of a Tetravalent Tris(cyclopentadienyl)cerium Alkoxide Complex

Antonino Gulino, Maurizio Casarin, Vincent P. Conticello, John G. Gaudiello, Heiko Mauermann, Ignazio Fragalá, Tobin J. Marks^*

^*Corresponding author for this work

Chemistry

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Abstract

The complex Cp₃Ce(O-i-Pr) (Cp = η⁵-C₅H₆) can be efficiently prepared from cerium tetrakis(isopropoxide) and Me₃SnCp. It is shown to be a genuine Ce(IV) complex by ¹H/¹³C NMR, elemental analysis, and cyclic voltammetry/controlled potential coulometry in Bu₄N⁺BF₄~/THF. The latter data indicate that Cp₃Ce(O-i-Pr) is a relatively strong oxidizing agent (E_1/2-+0.32 vs SSCE) and that one-electron reduction is both electrochemically and chemically reversible. Electronic structure calculations at the nonrelativistic Xα-DVM level suggest nonnegligible Ce-Cp f orbital covalency and yield transition state ionization energies in good agreement with He I/He II photoelectron spectra. There are substantial differences in redox properties and metal-ligand bonding between Cp₃Ce(O-i-Pr) and the other known tetravalent cerium organometallic complex Ce(C₈H₈)₂.

Original language	English (US)
Pages (from-to)	2360-2364
Number of pages	5
Journal	Organometallics
Volume	7
Issue number	11
DOIs	https://doi.org/10.1021/om00101a016
State	Published - Nov 1988

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Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Efficient Synthesis, Redox Characteristics, and Electronic Structure of a Tetravalent Tris(cyclopentadienyl)cerium Alkoxide Complex",

abstract = "The complex Cp3Ce(O-i-Pr) (Cp = η5-C5H6) can be efficiently prepared from cerium tetrakis(isopropoxide) and Me3SnCp. It is shown to be a genuine Ce(IV) complex by 1H/13C NMR, elemental analysis, and cyclic voltammetry/controlled potential coulometry in Bu4N+BF4~/THF. The latter data indicate that Cp3Ce(O-i-Pr) is a relatively strong oxidizing agent (E1/2-+0.32 vs SSCE) and that one-electron reduction is both electrochemically and chemically reversible. Electronic structure calculations at the nonrelativistic Xα-DVM level suggest nonnegligible Ce-Cp f orbital covalency and yield transition state ionization energies in good agreement with He I/He II photoelectron spectra. There are substantial differences in redox properties and metal-ligand bonding between Cp3Ce(O-i-Pr) and the other known tetravalent cerium organometallic complex Ce(C8H8)2.",

author = "Antonino Gulino and Maurizio Casarin and Conticello, {Vincent P.} and Gaudiello, {John G.} and Heiko Mauermann and Ignazio Fragal{\'a} and Marks, {Tobin J.}",

year = "1988",

month = nov,

doi = "10.1021/om00101a016",

language = "English (US)",

volume = "7",

pages = "2360--2364",

journal = "Organometallics",

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publisher = "American Chemical Society",

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T1 - Efficient Synthesis, Redox Characteristics, and Electronic Structure of a Tetravalent Tris(cyclopentadienyl)cerium Alkoxide Complex

AU - Gulino, Antonino

AU - Casarin, Maurizio

AU - Conticello, Vincent P.

AU - Gaudiello, John G.

AU - Mauermann, Heiko

AU - Fragalá, Ignazio

AU - Marks, Tobin J.

PY - 1988/11

Y1 - 1988/11

N2 - The complex Cp3Ce(O-i-Pr) (Cp = η5-C5H6) can be efficiently prepared from cerium tetrakis(isopropoxide) and Me3SnCp. It is shown to be a genuine Ce(IV) complex by 1H/13C NMR, elemental analysis, and cyclic voltammetry/controlled potential coulometry in Bu4N+BF4~/THF. The latter data indicate that Cp3Ce(O-i-Pr) is a relatively strong oxidizing agent (E1/2-+0.32 vs SSCE) and that one-electron reduction is both electrochemically and chemically reversible. Electronic structure calculations at the nonrelativistic Xα-DVM level suggest nonnegligible Ce-Cp f orbital covalency and yield transition state ionization energies in good agreement with He I/He II photoelectron spectra. There are substantial differences in redox properties and metal-ligand bonding between Cp3Ce(O-i-Pr) and the other known tetravalent cerium organometallic complex Ce(C8H8)2.

AB - The complex Cp3Ce(O-i-Pr) (Cp = η5-C5H6) can be efficiently prepared from cerium tetrakis(isopropoxide) and Me3SnCp. It is shown to be a genuine Ce(IV) complex by 1H/13C NMR, elemental analysis, and cyclic voltammetry/controlled potential coulometry in Bu4N+BF4~/THF. The latter data indicate that Cp3Ce(O-i-Pr) is a relatively strong oxidizing agent (E1/2-+0.32 vs SSCE) and that one-electron reduction is both electrochemically and chemically reversible. Electronic structure calculations at the nonrelativistic Xα-DVM level suggest nonnegligible Ce-Cp f orbital covalency and yield transition state ionization energies in good agreement with He I/He II photoelectron spectra. There are substantial differences in redox properties and metal-ligand bonding between Cp3Ce(O-i-Pr) and the other known tetravalent cerium organometallic complex Ce(C8H8)2.

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Efficient Synthesis, Redox Characteristics, and Electronic Structure of a Tetravalent Tris(cyclopentadienyl)cerium Alkoxide Complex

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