Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV)

Hannah  Stafford; Thomas Rookes; Elizabeth Wildman; Gabor Balazs; Ashley J Wooles; Manfred Scheer; Stephen Liddle

doi:10.1002/anie.201703870

Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV)

Hannah Stafford, Thomas Rookes, Elizabeth Wildman, Gabor Balazs, Ashley J Wooles, Manfred Scheer, Stephen Liddle

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

Abstract

The reaction of [Zr(TrenDMBS)(Cl)] [Zr1, TrenDMBS =
N(CH2CH2NSiMe2But)3] with NaPH2 gave the terminal parent phosphanide
complex [Zr(TrenDMBS)(PH2)] [Zr2, Zr-P = 2.685(2) Å]. Treatment of Zr2
with one equivalent of KCH2C6H5 and two equivalents of benzo-15-crown-5
ether (B15C5) afforded an unprecedented example outside of matrix
isolation of a structurally authenticated transition metal terminal parent
phosphinidene complex [Zr(TrenDMBS)(PH)][K(B15C5)2] [Zr3, Zr=P =
2.469(2) Å]. DFT calculations reveal a polarized-covalent Zr=P double
bond, with a Mayer bond order of 1.48, and together with IR spectroscopic
data also suggest an agostic-type Zr···HP interaction [∠ZrPH = 66.7°] which
is unexpectedly similar to that found in cryogenic spectroscopically
observed phosphinidene species. Surprisingly, computational data suggest
that the Zr=P linkage reported here is as polarized, and thus as covalent,
as essentially isostructural U=P and Th=P analogues.

Original language	English
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	26
Early online date	26 May 2017
DOIs	https://doi.org/10.1002/anie.201703870
Publication status	Published - 2017

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10.1002/anie.201703870

CCDC 1543842: Experimental Crystal Structure Determination
Stafford, H. (Contributor), Rookes, T. (Contributor), Wildman, E. (Contributor), Balazs, G. (Contributor), Wooles, A. J. (Contributor), Scheer, M. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1nthcb, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nthcb&sid=DataCite
Dataset
CCDC 1543843: Experimental Crystal Structure Determination
Stafford, H. (Contributor), Rookes, T. (Contributor), Wildman, E. (Contributor), Balazs, G. (Contributor), Wooles, A. J. (Contributor), Scheer, M. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1nthdc, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nthdc&sid=DataCite
Dataset

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@article{ddaa19671a204e6aae82fb6fe855fed1,

title = "Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV)",

abstract = "The reaction of [Zr(TrenDMBS)(Cl)] [Zr1, TrenDMBS =N(CH2CH2NSiMe2But)3] with NaPH2 gave the terminal parent phosphanidecomplex [Zr(TrenDMBS)(PH2)] [Zr2, Zr-P = 2.685(2) {\AA}]. Treatment of Zr2with one equivalent of KCH2C6H5 and two equivalents of benzo-15-crown-5ether (B15C5) afforded an unprecedented example outside of matrixisolation of a structurally authenticated transition metal terminal parentphosphinidene complex [Zr(TrenDMBS)(PH)][K(B15C5)2] [Zr3, Zr=P =2.469(2) {\AA}]. DFT calculations reveal a polarized-covalent Zr=P doublebond, with a Mayer bond order of 1.48, and together with IR spectroscopicdata also suggest an agostic-type Zr···HP interaction [∠ZrPH = 66.7°] whichis unexpectedly similar to that found in cryogenic spectroscopicallyobserved phosphinidene species. Surprisingly, computational data suggestthat the Zr=P linkage reported here is as polarized, and thus as covalent,as essentially isostructural U=P and Th=P analogues.",

author = "Hannah Stafford and Thomas Rookes and Elizabeth Wildman and Gabor Balazs and Wooles, {Ashley J} and Manfred Scheer and Stephen Liddle",

year = "2017",

doi = "10.1002/anie.201703870",

language = "English",

volume = "56",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley & Sons Ltd",

number = "26",

}

TY - JOUR

T1 - Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV)

AU - Stafford, Hannah

AU - Rookes, Thomas

AU - Wildman, Elizabeth

AU - Balazs, Gabor

AU - Wooles, Ashley J

AU - Scheer, Manfred

AU - Liddle, Stephen

PY - 2017

Y1 - 2017

N2 - The reaction of [Zr(TrenDMBS)(Cl)] [Zr1, TrenDMBS =N(CH2CH2NSiMe2But)3] with NaPH2 gave the terminal parent phosphanidecomplex [Zr(TrenDMBS)(PH2)] [Zr2, Zr-P = 2.685(2) Å]. Treatment of Zr2with one equivalent of KCH2C6H5 and two equivalents of benzo-15-crown-5ether (B15C5) afforded an unprecedented example outside of matrixisolation of a structurally authenticated transition metal terminal parentphosphinidene complex [Zr(TrenDMBS)(PH)][K(B15C5)2] [Zr3, Zr=P =2.469(2) Å]. DFT calculations reveal a polarized-covalent Zr=P doublebond, with a Mayer bond order of 1.48, and together with IR spectroscopicdata also suggest an agostic-type Zr···HP interaction [∠ZrPH = 66.7°] whichis unexpectedly similar to that found in cryogenic spectroscopicallyobserved phosphinidene species. Surprisingly, computational data suggestthat the Zr=P linkage reported here is as polarized, and thus as covalent,as essentially isostructural U=P and Th=P analogues.

AB - The reaction of [Zr(TrenDMBS)(Cl)] [Zr1, TrenDMBS =N(CH2CH2NSiMe2But)3] with NaPH2 gave the terminal parent phosphanidecomplex [Zr(TrenDMBS)(PH2)] [Zr2, Zr-P = 2.685(2) Å]. Treatment of Zr2with one equivalent of KCH2C6H5 and two equivalents of benzo-15-crown-5ether (B15C5) afforded an unprecedented example outside of matrixisolation of a structurally authenticated transition metal terminal parentphosphinidene complex [Zr(TrenDMBS)(PH)][K(B15C5)2] [Zr3, Zr=P =2.469(2) Å]. DFT calculations reveal a polarized-covalent Zr=P doublebond, with a Mayer bond order of 1.48, and together with IR spectroscopicdata also suggest an agostic-type Zr···HP interaction [∠ZrPH = 66.7°] whichis unexpectedly similar to that found in cryogenic spectroscopicallyobserved phosphinidene species. Surprisingly, computational data suggestthat the Zr=P linkage reported here is as polarized, and thus as covalent,as essentially isostructural U=P and Th=P analogues.

U2 - 10.1002/anie.201703870

DO - 10.1002/anie.201703870

M3 - Article

SN - 1433-7851

VL - 56

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 26

ER -

Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV)

Abstract

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Datasets

CCDC 1543842: Experimental Crystal Structure Determination

CCDC 1543843: Experimental Crystal Structure Determination

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