Formation of a Ce(IV) Oxo Complex via Inner Sphere Nitrate Reduction

Peter L. Damon; Guang  Wu; Nikolas Kaltsoyannis; Trevor W Hayton

doi:10.1021/jacs.6b07932

Formation of a Ce(IV) Oxo Complex via Inner Sphere Nitrate Reduction

Peter L. Damon, Guang Wu, Nikolas Kaltsoyannis, Trevor W Hayton

University of California, Santa Barbara

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Abstract

Reaction of Ce(NO3)3(THF)4 with Li3(THF)3(NN’3) (NN’3 = N(CH2CH2NR)3, R = SitBuMe2) in Et2O, in the presence of 12-crown-4, results in the formation of [Li(12-crown-4)][(NN’3)Ce(O)] (1) in 36% yield. This transformation proceeds via formation of a Ce(III) nitrate intermediate, [Li(12-crown-4)][(NN’3)Ce(κ2-O2NO)] (2), which undergoes inner sphere nitrate reduction. In addition, reaction of 1 with tBuMe2SiCl results in the formation of (NN’3)Ce(OSitBuMe2) (3), confirming the nucleophilic character of its oxo ligand. Natural bond orbital and quantum theory of atoms in molecules data reveal the Ce–O interaction in 1 to be significantly covalent, and strikingly similar to analogous U–O bonding.

Original language	English
Pages (from-to)	12743–12746
Journal	Journal of the American Chemical Society
Volume	138
Issue number	39
DOIs	https://doi.org/10.1021/jacs.6b07932
Publication status	Published - 13 Sept 2016

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CeO comm acceptedAccepted author manuscript, 516 KB

CCDC 1508768: Experimental Crystal Structure Determination
Damon, P. L. (Contributor), Wu, G. (Contributor), Kaltsoyannis, N. (Contributor) & Hayton, T. W. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2016
DOI: 10.5517/ccdc.csd.cc1mmzy5, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1mmzy5&sid=DataCite
Dataset
CCDC 1508767: Experimental Crystal Structure Determination
Damon, P. L. (Contributor), Wu, G. (Contributor), Kaltsoyannis, N. (Contributor) & Hayton, T. W. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2016
DOI: 10.5517/ccdc.csd.cc1mmzx4, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1mmzx4&sid=DataCite
Dataset
CCDC 1508766: Experimental Crystal Structure Determination
Damon, P. L. (Contributor), Wu, G. (Contributor), Kaltsoyannis, N. (Contributor) & Hayton, T. W. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2016
DOI: 10.5517/ccdc.csd.cc1mmzw3, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1mmzw3&sid=DataCite
Dataset

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@article{04e6a8f4c12442e2b24a163dbea27d12,

title = "Formation of a Ce(IV) Oxo Complex via Inner Sphere Nitrate Reduction",

abstract = "Reaction of Ce(NO3)3(THF)4 with Li3(THF)3(NN{\textquoteright}3) (NN{\textquoteright}3 = N(CH2CH2NR)3, R = SitBuMe2) in Et2O, in the presence of 12-crown-4, results in the formation of [Li(12-crown-4)][(NN{\textquoteright}3)Ce(O)] (1) in 36% yield. This transformation proceeds via formation of a Ce(III) nitrate intermediate, [Li(12-crown-4)][(NN{\textquoteright}3)Ce(κ2-O2NO)] (2), which undergoes inner sphere nitrate reduction. In addition, reaction of 1 with tBuMe2SiCl results in the formation of (NN{\textquoteright}3)Ce(OSitBuMe2) (3), confirming the nucleophilic character of its oxo ligand. Natural bond orbital and quantum theory of atoms in molecules data reveal the Ce–O interaction in 1 to be significantly covalent, and strikingly similar to analogous U–O bonding.",

author = "Damon, {Peter L.} and Guang Wu and Nikolas Kaltsoyannis and Hayton, {Trevor W}",

year = "2016",

month = sep,

day = "13",

doi = "10.1021/jacs.6b07932",

language = "English",

volume = "138",

pages = "12743–12746",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "39",

}

TY - JOUR

T1 - Formation of a Ce(IV) Oxo Complex via Inner Sphere Nitrate Reduction

AU - Damon, Peter L.

AU - Wu, Guang

AU - Kaltsoyannis, Nikolas

AU - Hayton, Trevor W

PY - 2016/9/13

Y1 - 2016/9/13

N2 - Reaction of Ce(NO3)3(THF)4 with Li3(THF)3(NN’3) (NN’3 = N(CH2CH2NR)3, R = SitBuMe2) in Et2O, in the presence of 12-crown-4, results in the formation of [Li(12-crown-4)][(NN’3)Ce(O)] (1) in 36% yield. This transformation proceeds via formation of a Ce(III) nitrate intermediate, [Li(12-crown-4)][(NN’3)Ce(κ2-O2NO)] (2), which undergoes inner sphere nitrate reduction. In addition, reaction of 1 with tBuMe2SiCl results in the formation of (NN’3)Ce(OSitBuMe2) (3), confirming the nucleophilic character of its oxo ligand. Natural bond orbital and quantum theory of atoms in molecules data reveal the Ce–O interaction in 1 to be significantly covalent, and strikingly similar to analogous U–O bonding.

AB - Reaction of Ce(NO3)3(THF)4 with Li3(THF)3(NN’3) (NN’3 = N(CH2CH2NR)3, R = SitBuMe2) in Et2O, in the presence of 12-crown-4, results in the formation of [Li(12-crown-4)][(NN’3)Ce(O)] (1) in 36% yield. This transformation proceeds via formation of a Ce(III) nitrate intermediate, [Li(12-crown-4)][(NN’3)Ce(κ2-O2NO)] (2), which undergoes inner sphere nitrate reduction. In addition, reaction of 1 with tBuMe2SiCl results in the formation of (NN’3)Ce(OSitBuMe2) (3), confirming the nucleophilic character of its oxo ligand. Natural bond orbital and quantum theory of atoms in molecules data reveal the Ce–O interaction in 1 to be significantly covalent, and strikingly similar to analogous U–O bonding.

U2 - 10.1021/jacs.6b07932

DO - 10.1021/jacs.6b07932

M3 - Article

SN - 0002-7863

VL - 138

SP - 12743

EP - 12746

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 39

ER -

Formation of a Ce(IV) Oxo Complex via Inner Sphere Nitrate Reduction

Abstract

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Datasets

CCDC 1508768: Experimental Crystal Structure Determination

CCDC 1508767: Experimental Crystal Structure Determination

CCDC 1508766: Experimental Crystal Structure Determination

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