Metal-free σ-bond metathesis in ammonia activation by a diazadiphosphapentalene

Jingjing Cui; Yongxin Li; Rakesh Ganguly; Anusiya Inthirarajah; Hajime Hirao; Rei Kinjo

doi:10.1021/ja509963m

Metal-free σ-bond metathesis in ammonia activation by a diazadiphosphapentalene

Jingjing Cui, Yongxin Li, Rakesh Ganguly, Anusiya Inthirarajah, Hajime Hirao^*, Rei Kinjo

^*Corresponding author for this work

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

81 Citations (Scopus)

Abstract

A diazadiphosphapentalene derivative 5 featuring a bent geometry with two phosphorus atoms at the bridgehead has been synthesized. Under mild conditions, compound 5 readily activated ammonia to afford 1-aza-2,3-diphospholene derivative 6 bearing an enamine group. The reaction is therefore viewed as a formal σ-bond metathesis between an N-H bond of ammonia and an endocyclic P-N bond of 5. Details of the reaction mechanism for ammonia activation as well as subsequent isomerization were explored by density functional theory calculations.

Original language	English
Pages (from-to)	16764-16767
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	136
Issue number	48
DOIs	https://doi.org/10.1021/ja509963m
Publication status	Published - Dec 3 2014
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2014 American Chemical Society.

ASJC Scopus Subject Areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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abstract = "A diazadiphosphapentalene derivative 5 featuring a bent geometry with two phosphorus atoms at the bridgehead has been synthesized. Under mild conditions, compound 5 readily activated ammonia to afford 1-aza-2,3-diphospholene derivative 6 bearing an enamine group. The reaction is therefore viewed as a formal σ-bond metathesis between an N-H bond of ammonia and an endocyclic P-N bond of 5. Details of the reaction mechanism for ammonia activation as well as subsequent isomerization were explored by density functional theory calculations.",

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AU - Cui, Jingjing

AU - Li, Yongxin

AU - Ganguly, Rakesh

AU - Inthirarajah, Anusiya

AU - Hirao, Hajime

AU - Kinjo, Rei

PY - 2014/12/3

Y1 - 2014/12/3

N2 - A diazadiphosphapentalene derivative 5 featuring a bent geometry with two phosphorus atoms at the bridgehead has been synthesized. Under mild conditions, compound 5 readily activated ammonia to afford 1-aza-2,3-diphospholene derivative 6 bearing an enamine group. The reaction is therefore viewed as a formal σ-bond metathesis between an N-H bond of ammonia and an endocyclic P-N bond of 5. Details of the reaction mechanism for ammonia activation as well as subsequent isomerization were explored by density functional theory calculations.

AB - A diazadiphosphapentalene derivative 5 featuring a bent geometry with two phosphorus atoms at the bridgehead has been synthesized. Under mild conditions, compound 5 readily activated ammonia to afford 1-aza-2,3-diphospholene derivative 6 bearing an enamine group. The reaction is therefore viewed as a formal σ-bond metathesis between an N-H bond of ammonia and an endocyclic P-N bond of 5. Details of the reaction mechanism for ammonia activation as well as subsequent isomerization were explored by density functional theory calculations.

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Metal-free σ-bond metathesis in ammonia activation by a diazadiphosphapentalene

Abstract

Bibliographical note

ASJC Scopus Subject Areas

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