Covalency in CeIV and UIV Halide and N-Heterocyclic Carbene Bonds

Polly L. Arnold; Zoe R. Turner; Nikolas Kaltsoyannis; Panagiota Pelekanaki; Ronan M. Bellabarba; Robert P. Tooze

doi:10.1002/chem.201001471

Covalency in Ce^IV and U^IV Halide and N-Heterocyclic Carbene Bonds

Polly L. Arnold, Zoe R. Turner, Nikolas Kaltsoyannis, Panagiota Pelekanaki, Ronan M. Bellabarba, Robert P. Tooze

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

Abstract

Oxidative halogenation with trityl chloride provides convenient access to Ce^IV and U^IV chloroamides [M(N{SiMe₃}₂)₃Cl] and their N-heterocyclic carbene derivatives, [M(L)(N-{SiMe₃}₂)₂Cl] (L= OCMe₂CH₂(CNCH₂CH₂NDipp) Dipp=2,6-iPr₂C₆H₃). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N{SiMe₃}₂)₂F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms-in-molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues.

Original language	English
Pages (from-to)	9623-9629
Number of pages	7
Journal	Chemistry - A European Journal
Volume	16
Issue number	31
Early online date	23 Jul 2010
DOIs	https://doi.org/10.1002/chem.201001471
Publication status	Published - 16 Aug 2010

Keywords / Materials (for Non-textual outputs)

actinides
computational chemistry
covalency
lanthanides
N-heterocyclic carbenes
DENSITY-FUNCTIONAL THEORY
LANTHANIDE(III)/ACTINIDE(III) DIFFERENTIATION
TETRAPYRROLE LIGANDS
CERIUM(IV) COMPLEXES
ELECTRONIC-STRUCTURE
SANDWICH COMPLEXES
PORPHYRIN LIGANDS
CRYSTAL-STRUCTURE
OXIDATION-STATE
METAL-COMPLEXES

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10.1002/chem.201001471

Covalency in CeIV and UIV Halide and N-Heterocyclic Carbene Bonds
Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. All rights reserved.
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title = "Covalency in CeIV and UIV Halide and N-Heterocyclic Carbene Bonds",

abstract = "Oxidative halogenation with trityl chloride provides convenient access to CeIV and UIV chloroamides [M(N\{SiMe3\}2)3Cl] and their N-heterocyclic carbene derivatives, [M(L)(N-\{SiMe3\}2)2Cl] (L= OCMe2CH2(CNCH2CH2NDipp) Dipp=2,6-iPr2C6H3). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N\{SiMe3\}2)2F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms-in-molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues.",

keywords = "actinides, computational chemistry, covalency, lanthanides, N-heterocyclic carbenes, DENSITY-FUNCTIONAL THEORY, LANTHANIDE(III)/ACTINIDE(III) DIFFERENTIATION, TETRAPYRROLE LIGANDS, CERIUM(IV) COMPLEXES, ELECTRONIC-STRUCTURE, SANDWICH COMPLEXES, PORPHYRIN LIGANDS, CRYSTAL-STRUCTURE, OXIDATION-STATE, METAL-COMPLEXES",

author = "Arnold, \{Polly L.\} and Turner, \{Zoe R.\} and Nikolas Kaltsoyannis and Panagiota Pelekanaki and Bellabarba, \{Ronan M.\} and Tooze, \{Robert P.\}",

year = "2010",

month = aug,

day = "16",

doi = "10.1002/chem.201001471",

language = "English",

volume = "16",

pages = "9623--9629",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley",

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TY - JOUR

T1 - Covalency in CeIV and UIV Halide and N-Heterocyclic Carbene Bonds

AU - Arnold, Polly L.

AU - Turner, Zoe R.

AU - Kaltsoyannis, Nikolas

AU - Pelekanaki, Panagiota

AU - Bellabarba, Ronan M.

AU - Tooze, Robert P.

PY - 2010/8/16

Y1 - 2010/8/16

N2 - Oxidative halogenation with trityl chloride provides convenient access to CeIV and UIV chloroamides [M(N{SiMe3}2)3Cl] and their N-heterocyclic carbene derivatives, [M(L)(N-{SiMe3}2)2Cl] (L= OCMe2CH2(CNCH2CH2NDipp) Dipp=2,6-iPr2C6H3). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N{SiMe3}2)2F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms-in-molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues.

AB - Oxidative halogenation with trityl chloride provides convenient access to CeIV and UIV chloroamides [M(N{SiMe3}2)3Cl] and their N-heterocyclic carbene derivatives, [M(L)(N-{SiMe3}2)2Cl] (L= OCMe2CH2(CNCH2CH2NDipp) Dipp=2,6-iPr2C6H3). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N{SiMe3}2)2F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms-in-molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues.

KW - actinides

KW - computational chemistry

KW - covalency

KW - lanthanides

KW - N-heterocyclic carbenes

KW - DENSITY-FUNCTIONAL THEORY

KW - LANTHANIDE(III)/ACTINIDE(III) DIFFERENTIATION

KW - TETRAPYRROLE LIGANDS

KW - CERIUM(IV) COMPLEXES

KW - ELECTRONIC-STRUCTURE

KW - SANDWICH COMPLEXES

KW - PORPHYRIN LIGANDS

KW - CRYSTAL-STRUCTURE

KW - OXIDATION-STATE

KW - METAL-COMPLEXES

UR - https://www.scopus.com/pages/publications/77955814230

U2 - 10.1002/chem.201001471

DO - 10.1002/chem.201001471

M3 - Article

SN - 0947-6539

VL - 16

SP - 9623

EP - 9629

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 31

ER -

Covalency in Ce^IV and U^IV Halide and N-Heterocyclic Carbene Bonds

Abstract

Keywords / Materials (for Non-textual outputs)

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