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Recent Developments in the Chemistry of N-Heterocyclic Phosphines

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Phosphorus Heterocycles II

Part of the book series: Topics in Heterocyclic Chemistry ((TOPICS,volume 21))

Abstract

This chapter gives a survey on five- and six-membered phosphorus–nitrogen heterocyclic compounds whose rings combine a phosphazene (>N–P = N–) or phosphazane (>N–P(X)–N<) unit with an unsaturated C2 or C3 building block. Representatives contain structurally diverse species like aromatic 1,3,2-diazaphosphinines and (benzo)-1,3,2-diazaphospholes, cationic counterparts of subvalent main-group carbene analogues like 1,3,2-diazaphospholenium ions and phosphenium-diketiminates, and neutral heterocycles like 1,3,2-diazaphospholenes featuring unusual structures and reactivities. The exploration of these species developed rapidly in the last two decades in the wake of cutting edge research on multiple bonding and low coordination in the chemistry of heavier main-group elements, and the discovery of stable carbenes. This review summarizes the elaboration of synthetic approaches for different types of N-heterocyclic phosphine derivatives, discusses their characterization by physical and computational methods which furnished a thorough understanding of structure and bonding, and finally highlights accomplishments in the exploration of the chemical properties at the border of classical organic heterocyclic chemistry and molecular inorganic chemistry.

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Notes

  1. 1.

    This is indeed corroborated by the use of similar condensation reactions for the synthesis of triazaphosphole derivatives; cf. [15].

  2. 2.

    The analogous reaction with AsCl3 gives likewise access to As heterocycles, cf. [19].

  3. 3.

    Condensation to yield the secondary product is often favored when solutions of NHPs are exposed to moist air or solvents and may result in formation of a mixture of 17 and 18.

Abbreviations

Bu:

Butyl

Cy:

Cyclohexyl

Dipp:

2,6-Diisopropylphenyl

Et:

Ethyl

Me:

Methyl

NHP:

N-heterocyclic phosphine @ 1,3,2-diazaphospholene

t-Bu:

tert-Butyl

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Acknowledgments

I am very much indebted to numerous coworkers and undergraduate students as well as many collaboration partners for their very engaged work and significant contributions to the chemistry outlined in this review. All their names appear in the list of references. I would also like to thank the Universität Stuttgart, Universität Bonn, and Deutsche Forschungsgemeinschaft for the financial support that was required to perform these studies.

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  1. Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart, Germany

    Dietrich Gudat

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Correspondence to Dietrich Gudat .

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  1. Dept. Chemistry, University of Rajasthan, Jaipur, 302004, India

    Raj K. Bansal

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Gudat, D. (2010). Recent Developments in the Chemistry of N-Heterocyclic Phosphines. In: Bansal, R. (eds) Phosphorus Heterocycles II. Topics in Heterocyclic Chemistry, vol 21. Springer, Berlin, Heidelberg. https://doi.org/10.1007/7081_2009_5

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