Crystalline Diuranium-Phosphinidiide and -μ-Phosphido Complexes with Symmetric and Asymmetric UPU Cores

Thomas Rookes; Benedict Gardner; Gabor Balazs; Matthew Gregson; Floriana Tuna; Ashley Wooles; Manfred Scheer; Stephen Liddle

doi:10.1002/anie.201706002

Crystalline Diuranium-Phosphinidiide and -μ-Phosphido Complexes with Symmetric and Asymmetric UPU Cores

Thomas Rookes, Benedict Gardner, Gabor Balazs, Matthew Gregson, Floriana Tuna, Ashley Wooles, Manfred Scheer, Stephen Liddle

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

Abstract

Reaction of [U(TrenTIPS)(PH2)] (1, TrenTIPS = N(CH2CH2NSiPri 3)3) with C6H5CH2K and [U(TrenTIPS)(THF)][BPh4] (2) afforded a rare diuranium-parent-phosphinidiide complex [{U(TrenTIPS)}2(μ-PH)] (3). Treatment of 3 with C6H5CH2K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium-μ- phosphido complex [{U(TrenTIPS)}2(μ-P)][K(B15C5)2] (4). Alternatively, reaction of [U(TrenTIPS)(PH)][Na(12C4)2] (5, 12C4 = 12-crown-4 ether) with [U{N(CH2CH2NSiMe2But)2CH2CH2NSi(Me)(CH2)(But)}] (6) produced the diuranium-μ-phosphido complex [{U(TrenTIPS)}(μ- P){U(TrenDMBS)}][Na(12C4)2] [7, TrenDMBS = N(CH2CH2NSiMe2But)3]. Compounds 4 and 7 are unprecedented examples of uranium-phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium-phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles.

Original language	English
Pages (from-to)	10495-10500
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	35
Early online date	24 Jul 2017
DOIs	https://doi.org/10.1002/anie.201706002
Publication status	Published - 21 Aug 2017

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CCDC 1554771: Experimental Crystal Structure Determination
Rookes, T. (Contributor), Gardner, B. (Contributor), Balazs, G. (Contributor), Gregson, M. (Contributor), Tuna, F. (Contributor), Wooles, A. (Contributor), Scheer, M. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1p5vxm, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p5vxm&sid=DataCite
Dataset
CCDC 1554773: Experimental Crystal Structure Determination
Rookes, T. (Contributor), Gardner, B. (Contributor), Balazs, G. (Contributor), Gregson, M. (Contributor), Tuna, F. (Contributor), Wooles, A. (Contributor), Scheer, M. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1p5vzp, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p5vzp&sid=DataCite
Dataset
CCDC 1554772: Experimental Crystal Structure Determination
Rookes, T. (Contributor), Gardner, B. (Contributor), Balazs, G. (Contributor), Gregson, M. (Contributor), Tuna, F. (Contributor), Wooles, A. (Contributor), Scheer, M. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1p5vyn, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p5vyn&sid=DataCite
Dataset

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@article{d75d073469154e7ab7397c41352c2bb5,

title = "Crystalline Diuranium-Phosphinidiide and -μ-Phosphido Complexes with Symmetric and Asymmetric UPU Cores",

abstract = "Reaction of [U(TrenTIPS)(PH2)] (1, TrenTIPS = N(CH2CH2NSiPri 3)3) with C6H5CH2K and [U(TrenTIPS)(THF)][BPh4] (2) afforded a rare diuranium-parent-phosphinidiide complex [{U(TrenTIPS)}2(μ-PH)] (3). Treatment of 3 with C6H5CH2K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium-μ- phosphido complex [{U(TrenTIPS)}2(μ-P)][K(B15C5)2] (4). Alternatively, reaction of [U(TrenTIPS)(PH)][Na(12C4)2] (5, 12C4 = 12-crown-4 ether) with [U{N(CH2CH2NSiMe2But)2CH2CH2NSi(Me)(CH2)(But)}] (6) produced the diuranium-μ-phosphido complex [{U(TrenTIPS)}(μ- P){U(TrenDMBS)}][Na(12C4)2] [7, TrenDMBS = N(CH2CH2NSiMe2But)3]. Compounds 4 and 7 are unprecedented examples of uranium-phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium-phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles.",

author = "Thomas Rookes and Benedict Gardner and Gabor Balazs and Matthew Gregson and Floriana Tuna and Ashley Wooles and Manfred Scheer and Stephen Liddle",

year = "2017",

month = aug,

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doi = "10.1002/anie.201706002",

language = "English",

volume = "56",

pages = "10495--10500",

journal = "Angewandte Chemie. International Edition",

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publisher = "John Wiley & Sons Ltd",

number = "35",

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T1 - Crystalline Diuranium-Phosphinidiide and -μ-Phosphido Complexes with Symmetric and Asymmetric UPU Cores

AU - Rookes, Thomas

AU - Gardner, Benedict

AU - Balazs, Gabor

AU - Gregson, Matthew

AU - Tuna, Floriana

AU - Wooles, Ashley

AU - Scheer, Manfred

AU - Liddle, Stephen

PY - 2017/8/21

Y1 - 2017/8/21

N2 - Reaction of [U(TrenTIPS)(PH2)] (1, TrenTIPS = N(CH2CH2NSiPri 3)3) with C6H5CH2K and [U(TrenTIPS)(THF)][BPh4] (2) afforded a rare diuranium-parent-phosphinidiide complex [{U(TrenTIPS)}2(μ-PH)] (3). Treatment of 3 with C6H5CH2K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium-μ- phosphido complex [{U(TrenTIPS)}2(μ-P)][K(B15C5)2] (4). Alternatively, reaction of [U(TrenTIPS)(PH)][Na(12C4)2] (5, 12C4 = 12-crown-4 ether) with [U{N(CH2CH2NSiMe2But)2CH2CH2NSi(Me)(CH2)(But)}] (6) produced the diuranium-μ-phosphido complex [{U(TrenTIPS)}(μ- P){U(TrenDMBS)}][Na(12C4)2] [7, TrenDMBS = N(CH2CH2NSiMe2But)3]. Compounds 4 and 7 are unprecedented examples of uranium-phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium-phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles.

AB - Reaction of [U(TrenTIPS)(PH2)] (1, TrenTIPS = N(CH2CH2NSiPri 3)3) with C6H5CH2K and [U(TrenTIPS)(THF)][BPh4] (2) afforded a rare diuranium-parent-phosphinidiide complex [{U(TrenTIPS)}2(μ-PH)] (3). Treatment of 3 with C6H5CH2K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium-μ- phosphido complex [{U(TrenTIPS)}2(μ-P)][K(B15C5)2] (4). Alternatively, reaction of [U(TrenTIPS)(PH)][Na(12C4)2] (5, 12C4 = 12-crown-4 ether) with [U{N(CH2CH2NSiMe2But)2CH2CH2NSi(Me)(CH2)(But)}] (6) produced the diuranium-μ-phosphido complex [{U(TrenTIPS)}(μ- P){U(TrenDMBS)}][Na(12C4)2] [7, TrenDMBS = N(CH2CH2NSiMe2But)3]. Compounds 4 and 7 are unprecedented examples of uranium-phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium-phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles.

U2 - 10.1002/anie.201706002

DO - 10.1002/anie.201706002

M3 - Article

VL - 56

SP - 10495

EP - 10500

JO - Angewandte Chemie. International Edition

JF - Angewandte Chemie. International Edition

SN - 1433-7851

IS - 35

ER -

Crystalline Diuranium-Phosphinidiide and -μ-Phosphido Complexes with Symmetric and Asymmetric UPU Cores

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CCDC 1554771: Experimental Crystal Structure Determination

CCDC 1554773: Experimental Crystal Structure Determination

CCDC 1554772: Experimental Crystal Structure Determination

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