Carbamoylphosphinidene: A Phosphorus Analogue of Carbonyl Nitrene

Bo Lu; Junjie Jiang; Andrew R. Jupp; Jose M. Goicoechea; Shihua Liu; Zhongshu Li; Mingfei Zhou; Xiaoqing Zeng; Lina Wang

doi:10.1021/jacs.4c06016

Carbamoylphosphinidene: A Phosphorus Analogue of Carbonyl Nitrene

Bo Lu
, Junjie Jiang
, Andrew R. Jupp
, Jose M. Goicoechea^*
, Shihua Liu
, Zhongshu Li
, Mingfei Zhou
, Xiaoqing Zeng^*
, Lina Wang

^*Corresponding author for this work

Chemistry

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

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Abstract

Carbonyl nitrenes are versatile intermediates that have been extensively characterized; however, their phosphorus analogues remain largely unknown. Herein, we report the observation of a rare example of carbonyl phosphinidene NH₂C(O)P, which was generated through the photolytic (193 nm) dehydrogenation of phosphinecarboxamide (NH₂C(O)PH₂₎ in a solid N₂-matrix at 12 K. The characterization of NH₂C(O)P in the triplet ground state with matrix-isolation IR and ultraviolet–visible (UV–vis) spectroscopy is supported by comprehensive isotope labeling experiments (D and ¹⁵N) and quantum chemical calculations. Upon visible-light irradiation at 680 nm, NH₂C(O)P inserts into dihydrogen by the reformation of NH₂C(O)PH₂ with concomitant isomerization to the more stable aminophosphaketene (NH₂PCO). Additionally, the photoisomerization of NH₂C(O)PH₂ to NH₂C(OH) = PH along with decomposition by yielding hydrogen-bonded complexes HNCO···PH₃ and HPCO···NH₃ has been observed in the matrix.

Original language	English
Pages (from-to)	18699–18705
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	146
Issue number	27
Early online date	29 Jun 2024
DOIs	https://doi.org/10.1021/jacs.4c06016
Publication status	Published - 10 Jul 2024

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10.1021/jacs.4c06016

LuB2024Carbamoylphosphinidene
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see: https://doi.org/10.1021/jacs.4c06016
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@article{e6cfbee86b36459f84748f4b8d11a3e3,

title = "Carbamoylphosphinidene: A Phosphorus Analogue of Carbonyl Nitrene",

abstract = "Carbonyl nitrenes are versatile intermediates that have been extensively characterized; however, their phosphorus analogues remain largely unknown. Herein, we report the observation of a rare example of carbonyl phosphinidene NH2C(O)P, which was generated through the photolytic (193 nm) dehydrogenation of phosphinecarboxamide (NH2C(O)PH2) in a solid N2-matrix at 12 K. The characterization of NH2C(O)P in the triplet ground state with matrix-isolation IR and ultraviolet–visible (UV–vis) spectroscopy is supported by comprehensive isotope labeling experiments (D and 15N) and quantum chemical calculations. Upon visible-light irradiation at 680 nm, NH2C(O)P inserts into dihydrogen by the reformation of NH2C(O)PH2 with concomitant isomerization to the more stable aminophosphaketene (NH2PCO). Additionally, the photoisomerization of NH2C(O)PH2 to NH2C(OH) = PH along with decomposition by yielding hydrogen-bonded complexes HNCO···PH3 and HPCO···NH3 has been observed in the matrix.",

author = "Bo Lu and Junjie Jiang and Jupp, \{Andrew R.\} and Goicoechea, \{Jose M.\} and Shihua Liu and Zhongshu Li and Mingfei Zhou and Xiaoqing Zeng and Lina Wang",

year = "2024",

month = jul,

day = "10",

doi = "10.1021/jacs.4c06016",

language = "English",

volume = "146",

pages = "18699–18705",

journal = "Journal of the American Chemical Society",

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TY - JOUR

T1 - Carbamoylphosphinidene

T2 - A Phosphorus Analogue of Carbonyl Nitrene

AU - Lu, Bo

AU - Jiang, Junjie

AU - Jupp, Andrew R.

AU - Goicoechea, Jose M.

AU - Liu, Shihua

AU - Li, Zhongshu

AU - Zhou, Mingfei

AU - Zeng, Xiaoqing

AU - Wang, Lina

PY - 2024/7/10

Y1 - 2024/7/10

N2 - Carbonyl nitrenes are versatile intermediates that have been extensively characterized; however, their phosphorus analogues remain largely unknown. Herein, we report the observation of a rare example of carbonyl phosphinidene NH2C(O)P, which was generated through the photolytic (193 nm) dehydrogenation of phosphinecarboxamide (NH2C(O)PH2) in a solid N2-matrix at 12 K. The characterization of NH2C(O)P in the triplet ground state with matrix-isolation IR and ultraviolet–visible (UV–vis) spectroscopy is supported by comprehensive isotope labeling experiments (D and 15N) and quantum chemical calculations. Upon visible-light irradiation at 680 nm, NH2C(O)P inserts into dihydrogen by the reformation of NH2C(O)PH2 with concomitant isomerization to the more stable aminophosphaketene (NH2PCO). Additionally, the photoisomerization of NH2C(O)PH2 to NH2C(OH) = PH along with decomposition by yielding hydrogen-bonded complexes HNCO···PH3 and HPCO···NH3 has been observed in the matrix.

AB - Carbonyl nitrenes are versatile intermediates that have been extensively characterized; however, their phosphorus analogues remain largely unknown. Herein, we report the observation of a rare example of carbonyl phosphinidene NH2C(O)P, which was generated through the photolytic (193 nm) dehydrogenation of phosphinecarboxamide (NH2C(O)PH2) in a solid N2-matrix at 12 K. The characterization of NH2C(O)P in the triplet ground state with matrix-isolation IR and ultraviolet–visible (UV–vis) spectroscopy is supported by comprehensive isotope labeling experiments (D and 15N) and quantum chemical calculations. Upon visible-light irradiation at 680 nm, NH2C(O)P inserts into dihydrogen by the reformation of NH2C(O)PH2 with concomitant isomerization to the more stable aminophosphaketene (NH2PCO). Additionally, the photoisomerization of NH2C(O)PH2 to NH2C(OH) = PH along with decomposition by yielding hydrogen-bonded complexes HNCO···PH3 and HPCO···NH3 has been observed in the matrix.

U2 - 10.1021/jacs.4c06016

DO - 10.1021/jacs.4c06016

M3 - Article

SN - 0002-7863

VL - 146

SP - 18699

EP - 18705

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 27

ER -

Carbamoylphosphinidene: A Phosphorus Analogue of Carbonyl Nitrene

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