Synthesis and structure of a terminal uranium nitride complex

David M. King; Floriana Tuna; Eric J L McInnes; Jonathan McMaster; William Lewis; Alexander J. Blake; Stephen T. Liddle

doi:10.1126/science.1223488

Synthesis and structure of a terminal uranium nitride complex

David M. King, Floriana Tuna, Eric J L McInnes, Jonathan McMaster, William Lewis, Alexander J. Blake, Stephen T. Liddle

The University of Manchester

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

Abstract

The terminal uranium nitride linkage is a fundamental target in the study of f-orbital participation in metal-ligand multiple bonding but has previously eluded characterization in an isolable molecule. Here, we report the preparation of the terminal uranium(V) nitride complex [UN(Tren TIPS)][Na(12- crown-4) 2] {in which Tren TIPS = [N(CH 2CH 2NSiPr i 3) 3] 3- and Pr i = CH(CH 3) 2} by reaction of the uranium(III) complex [U(Tren TIPS)] with sodium azide followed by abstraction and encapsulation of the sodium cation by the polydentate crown ether 12-crown-4. Single-crystal x-ray diffraction reveals a uranium-terminal nitride bond length of 1.825(15) angstroms (where 15 is the standard uncertainty). The structural assignment is supported by means of 15N-isotopic labeling, electronic absorption spectroscopy, magnetometry, electronic structure calculations, elemental analyses, and liberation of ammonia after treatment with water.

Original language	English
Pages (from-to)	717-720
Number of pages	3
Journal	Science
Volume	337
Issue number	6095
DOIs	https://doi.org/10.1126/science.1223488
Publication status	Published - 10 Aug 2012

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10.1126/science.1223488

CCDC 876424: Experimental Crystal Structure Determination
King, D. M. (Contributor), Tuna, F. (Contributor), Mcinnes, E. (Contributor), McMaster, J. (Contributor), Lewis, W. (Contributor), Blake, A. J. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2012
DOI: 10.5517/ccydzr1, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccydzr1&sid=DataCite
Dataset
CCDC 876421: Experimental Crystal Structure Determination
King, D. M. (Contributor), Tuna, F. (Contributor), Mcinnes, E. (Contributor), McMaster, J. (Contributor), Lewis, W. (Contributor), Blake, A. J. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2013
DOI: 10.5517/ccydzny, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccydzny&sid=DataCite
Dataset
CCDC 876423: Experimental Crystal Structure Determination
King, D. M. (Contributor), Tuna, F. (Contributor), Mcinnes, E. (Contributor), McMaster, J. (Contributor), Lewis, W. (Contributor), Blake, A. J. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2013
DOI: 10.5517/ccydzq0, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccydzq0&sid=DataCite
Dataset

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@article{760dba9ccb9048f386c7d5e46f29af2f,

title = "Synthesis and structure of a terminal uranium nitride complex",

abstract = "The terminal uranium nitride linkage is a fundamental target in the study of f-orbital participation in metal-ligand multiple bonding but has previously eluded characterization in an isolable molecule. Here, we report the preparation of the terminal uranium(V) nitride complex [UN(Tren TIPS)][Na(12- crown-4) 2] {in which Tren TIPS = [N(CH 2CH 2NSiPr i 3) 3] 3- and Pr i = CH(CH 3) 2} by reaction of the uranium(III) complex [U(Tren TIPS)] with sodium azide followed by abstraction and encapsulation of the sodium cation by the polydentate crown ether 12-crown-4. Single-crystal x-ray diffraction reveals a uranium-terminal nitride bond length of 1.825(15) angstroms (where 15 is the standard uncertainty). The structural assignment is supported by means of 15N-isotopic labeling, electronic absorption spectroscopy, magnetometry, electronic structure calculations, elemental analyses, and liberation of ammonia after treatment with water.",

author = "King, {David M.} and Floriana Tuna and McInnes, {Eric J L} and Jonathan McMaster and William Lewis and Blake, {Alexander J.} and Liddle, {Stephen T.}",

year = "2012",

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doi = "10.1126/science.1223488",

language = "English",

volume = "337",

pages = "717--720",

journal = "Science",

issn = "0036-8075",

publisher = "American Association for the Advancement of Science (A A A S)",

number = "6095",

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TY - JOUR

T1 - Synthesis and structure of a terminal uranium nitride complex

AU - King, David M.

AU - Tuna, Floriana

AU - McInnes, Eric J L

AU - McMaster, Jonathan

AU - Lewis, William

AU - Blake, Alexander J.

AU - Liddle, Stephen T.

PY - 2012/8/10

Y1 - 2012/8/10

N2 - The terminal uranium nitride linkage is a fundamental target in the study of f-orbital participation in metal-ligand multiple bonding but has previously eluded characterization in an isolable molecule. Here, we report the preparation of the terminal uranium(V) nitride complex [UN(Tren TIPS)][Na(12- crown-4) 2] {in which Tren TIPS = [N(CH 2CH 2NSiPr i 3) 3] 3- and Pr i = CH(CH 3) 2} by reaction of the uranium(III) complex [U(Tren TIPS)] with sodium azide followed by abstraction and encapsulation of the sodium cation by the polydentate crown ether 12-crown-4. Single-crystal x-ray diffraction reveals a uranium-terminal nitride bond length of 1.825(15) angstroms (where 15 is the standard uncertainty). The structural assignment is supported by means of 15N-isotopic labeling, electronic absorption spectroscopy, magnetometry, electronic structure calculations, elemental analyses, and liberation of ammonia after treatment with water.

AB - The terminal uranium nitride linkage is a fundamental target in the study of f-orbital participation in metal-ligand multiple bonding but has previously eluded characterization in an isolable molecule. Here, we report the preparation of the terminal uranium(V) nitride complex [UN(Tren TIPS)][Na(12- crown-4) 2] {in which Tren TIPS = [N(CH 2CH 2NSiPr i 3) 3] 3- and Pr i = CH(CH 3) 2} by reaction of the uranium(III) complex [U(Tren TIPS)] with sodium azide followed by abstraction and encapsulation of the sodium cation by the polydentate crown ether 12-crown-4. Single-crystal x-ray diffraction reveals a uranium-terminal nitride bond length of 1.825(15) angstroms (where 15 is the standard uncertainty). The structural assignment is supported by means of 15N-isotopic labeling, electronic absorption spectroscopy, magnetometry, electronic structure calculations, elemental analyses, and liberation of ammonia after treatment with water.

U2 - 10.1126/science.1223488

DO - 10.1126/science.1223488

M3 - Article

SN - 0036-8075

VL - 337

SP - 717

EP - 720

JO - Science

JF - Science

IS - 6095

ER -

Synthesis and structure of a terminal uranium nitride complex

Abstract

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Datasets

CCDC 876424: Experimental Crystal Structure Determination

CCDC 876421: Experimental Crystal Structure Determination

CCDC 876423: Experimental Crystal Structure Determination

Cite this