Triamidoamine-uranium(IV)-stabilized terminal parent phosphide and phosphinidene complexes

Benedict M. Gardner; Gábor Balázs; Manfred Scheer; Floriana Tuna; Eric J L McInnes; Jonathan McMaster; William Lewis; Alexander J. Blake; Stephen T. Liddle

doi:10.1002/anie.201400798

Triamidoamine-uranium(IV)-stabilized terminal parent phosphide and phosphinidene complexes

Benedict M. Gardner, Gábor Balázs, Manfred Scheer, Floriana Tuna, Eric J L McInnes, Jonathan McMaster, William Lewis, Alexander J. Blake, Stephen T. Liddle

The University of Manchester

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Abstract

Reaction of [U(TrenTIPS)(THF)][BPh4] (1; Tren TIPS=N{CH2CH2NSi(iPr)3} 3) with NaPH2 afforded the novel f-block terminal parent phosphide complex [U(TrenTIPS)(PH2)] (2; U-P=2.883(2)?Å). Treatment of 2 with one equivalent of KCH 2C6H5 and two equivalents of benzo-15-crown-5 ether (B15C5) afforded the unprecedented metal-stabilized terminal parent phosphinidene complex [U(TrenTIPS)(PH)][K(B15C5)2] (4; UP=2.613(2)?Å). DFT calculations reveal a polarized-covalent UP bond with a Mayer bond order of 1.92. Straightforward deprotonation of the first f-block terminal parent phosphide complex and potassium abstraction results in the isolation of an unprecedented structurally authenticated metal-stabilized terminal parent phosphinidene complex. B15C5=benzo-15-crown-5 ether. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Original language	English
Pages (from-to)	4484-4488
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	53
Issue number	17
DOIs	https://doi.org/10.1002/anie.201400798
Publication status	Published - 22 Apr 2014

Keywords

density functional calculations
multiple bonds
phosphides
phosphinidene
uranium

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@article{8c4679ee411f40b288f037208adfe246,

title = "Triamidoamine-uranium(IV)-stabilized terminal parent phosphide and phosphinidene complexes",

abstract = "Reaction of [U(TrenTIPS)(THF)][BPh4] (1; Tren TIPS=N{CH2CH2NSi(iPr)3} 3) with NaPH2 afforded the novel f-block terminal parent phosphide complex [U(TrenTIPS)(PH2)] (2; U-P=2.883(2)?{\AA}). Treatment of 2 with one equivalent of KCH 2C6H5 and two equivalents of benzo-15-crown-5 ether (B15C5) afforded the unprecedented metal-stabilized terminal parent phosphinidene complex [U(TrenTIPS)(PH)][K(B15C5)2] (4; UP=2.613(2)?{\AA}). DFT calculations reveal a polarized-covalent UP bond with a Mayer bond order of 1.92. Straightforward deprotonation of the first f-block terminal parent phosphide complex and potassium abstraction results in the isolation of an unprecedented structurally authenticated metal-stabilized terminal parent phosphinidene complex. B15C5=benzo-15-crown-5 ether. {\textcopyright} 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

keywords = "density functional calculations, multiple bonds, phosphides, phosphinidene, uranium",

author = "Gardner, {Benedict M.} and G{\'a}bor Bal{\'a}zs and Manfred Scheer and Floriana Tuna and McInnes, {Eric J L} and Jonathan McMaster and William Lewis and Blake, {Alexander J.} and Liddle, {Stephen T.}",

note = "Times Cited: 4",

year = "2014",

month = apr,

day = "22",

doi = "10.1002/anie.201400798",

language = "English",

volume = "53",

pages = "4484--4488",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley & Sons Ltd",

number = "17",

}

TY - JOUR

T1 - Triamidoamine-uranium(IV)-stabilized terminal parent phosphide and phosphinidene complexes

AU - Gardner, Benedict M.

AU - Balázs, Gábor

AU - Scheer, Manfred

AU - Tuna, Floriana

AU - McInnes, Eric J L

AU - McMaster, Jonathan

AU - Lewis, William

AU - Blake, Alexander J.

AU - Liddle, Stephen T.

N1 - Times Cited: 4

PY - 2014/4/22

Y1 - 2014/4/22

N2 - Reaction of [U(TrenTIPS)(THF)][BPh4] (1; Tren TIPS=N{CH2CH2NSi(iPr)3} 3) with NaPH2 afforded the novel f-block terminal parent phosphide complex [U(TrenTIPS)(PH2)] (2; U-P=2.883(2)?Å). Treatment of 2 with one equivalent of KCH 2C6H5 and two equivalents of benzo-15-crown-5 ether (B15C5) afforded the unprecedented metal-stabilized terminal parent phosphinidene complex [U(TrenTIPS)(PH)][K(B15C5)2] (4; UP=2.613(2)?Å). DFT calculations reveal a polarized-covalent UP bond with a Mayer bond order of 1.92. Straightforward deprotonation of the first f-block terminal parent phosphide complex and potassium abstraction results in the isolation of an unprecedented structurally authenticated metal-stabilized terminal parent phosphinidene complex. B15C5=benzo-15-crown-5 ether. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

AB - Reaction of [U(TrenTIPS)(THF)][BPh4] (1; Tren TIPS=N{CH2CH2NSi(iPr)3} 3) with NaPH2 afforded the novel f-block terminal parent phosphide complex [U(TrenTIPS)(PH2)] (2; U-P=2.883(2)?Å). Treatment of 2 with one equivalent of KCH 2C6H5 and two equivalents of benzo-15-crown-5 ether (B15C5) afforded the unprecedented metal-stabilized terminal parent phosphinidene complex [U(TrenTIPS)(PH)][K(B15C5)2] (4; UP=2.613(2)?Å). DFT calculations reveal a polarized-covalent UP bond with a Mayer bond order of 1.92. Straightforward deprotonation of the first f-block terminal parent phosphide complex and potassium abstraction results in the isolation of an unprecedented structurally authenticated metal-stabilized terminal parent phosphinidene complex. B15C5=benzo-15-crown-5 ether. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

KW - density functional calculations

KW - multiple bonds

KW - phosphides

KW - phosphinidene

KW - uranium

U2 - 10.1002/anie.201400798

DO - 10.1002/anie.201400798

M3 - Article

SN - 1433-7851

VL - 53

SP - 4484

EP - 4488

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 17

ER -

Triamidoamine-uranium(IV)-stabilized terminal parent phosphide and phosphinidene complexes

Abstract

Keywords

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CCDC 982436: Experimental Crystal Structure Determination

CCDC 982437: Experimental Crystal Structure Determination

CCDC 982435: Experimental Crystal Structure Determination

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Triamidoamine-uranium(IV)-stabilized terminal parent phosphide and phosphinidene complexes

Abstract

Keywords

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Datasets

CCDC 982436: Experimental Crystal Structure Determination

CCDC 982437: Experimental Crystal Structure Determination

CCDC 982435: Experimental Crystal Structure Determination

Cite this