Chemistry – A European Journal

Volume 22, Issue 49 p. 17562-17565

Communication

A Masked Phosphinidene Trapped in a Fluxional NCN Pincer

Dr. Jakub Hyvl,

Dr. Jakub Hyvl

Department of Chemistry, University of Hawai'i at Mānoa, 2545 McCarthy Mall, Honolulu, HI, 96822 USA

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M. Sc. Wesley Y. Yoshida,

M. Sc. Wesley Y. Yoshida

Department of Chemistry, University of Hawai'i at Mānoa, 2545 McCarthy Mall, Honolulu, HI, 96822 USA

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Prof. Dr. Arnold L. Rheingold,

Prof. Dr. Arnold L. Rheingold

Department of Chemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA, 92093 USA

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Prof. Dr. Russell P. Hughes,

Prof. Dr. Russell P. Hughes

Department of Chemistry, Dartmouth College, 6128 Burke Laboratory, Hanover, NH, 03755 USA

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Prof. Dr. Matthew F. Cain,

Corresponding Author

Prof. Dr. Matthew F. Cain

[email protected]

Department of Chemistry, University of Hawai'i at Mānoa, 2545 McCarthy Mall, Honolulu, HI, 96822 USA

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Dr. Jakub Hyvl,

Dr. Jakub Hyvl

Department of Chemistry, University of Hawai'i at Mānoa, 2545 McCarthy Mall, Honolulu, HI, 96822 USA

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M. Sc. Wesley Y. Yoshida,

M. Sc. Wesley Y. Yoshida

Department of Chemistry, University of Hawai'i at Mānoa, 2545 McCarthy Mall, Honolulu, HI, 96822 USA

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Prof. Dr. Arnold L. Rheingold,

Prof. Dr. Arnold L. Rheingold

Department of Chemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA, 92093 USA

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Prof. Dr. Russell P. Hughes,

Prof. Dr. Russell P. Hughes

Department of Chemistry, Dartmouth College, 6128 Burke Laboratory, Hanover, NH, 03755 USA

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Prof. Dr. Matthew F. Cain,

Corresponding Author

Prof. Dr. Matthew F. Cain

[email protected]

Department of Chemistry, University of Hawai'i at Mānoa, 2545 McCarthy Mall, Honolulu, HI, 96822 USA

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First published: 21 September 2016

https://doi.org/10.1002/chem.201604415

Citations: 42

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Graphical Abstract

The bell tolls for P: The trapping of a phosphinidene (R−P) in an NCN pincer is presented. In the solid state, the phosphinidene is coordinated by one adjacent N atom featuring to give a five-membered ring with some aromatic character. Equilibration of the two N ligands occurs rapidly in solution via a “bell-clapper”-type process.

Abstract

The trapping of a phosphinidene (R-P) in an NCN pincer is presented. Stabilized phosphinidene 1 was characterized by ³¹P{¹H}, ¹H, and ¹³C{¹H} NMR spectroscopy, exhibiting an averaged C_2v symmetry in solution between −60 and 60 °C. In the solid state, the phosphinidene is coordinated by one adjacent N atom featuring a formal P−N bond (1.757(2) Å) to give a five-membered ring with some aromatic character, confirmed by DFT calculations (B3LYP-D3/6-311G**++) to be the ground-state structure. Equilibration of the two N ligands occurs rapidly in solution via a “bell-clapper”-type process through an associative symmetric transition state calculated to lie 4.0 kcal mol⁻¹ above the ground state.

Supporting Information

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Volume22, Issue49

December 5, 2016

Pages 17562-17565

A Masked Phosphinidene Trapped in a Fluxional NCN Pincer

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A Masked Phosphinidene Trapped in a Fluxional NCN Pincer

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