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Cooperative Reactivity by Pincer-Type Complexes Possessing Secondary Coordination Sphere

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Metal-Ligand Co-operativity

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 68))

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Abstract

Pincer complexes represent a family of potent compounds having a tremendous number of manifold applications in organometallic chemistry, synthesis, catalysis, materials science, and bioinorganic chemistry. This chapter overviews the recent developments in the chemistry and catalytic applications of pincer complexes incorporating secondary coordination sphere or an appended functionality that can interact with the catalytic center or can modulate its reactivity via secondary substrate-catalyst interactions. Combining the concepts of modular and stable pincer ligands and secondary interactions provides excellent opportunities for fine-tuning the properties of a coordinated metal center and, consequently, attracts considerable interest.

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Abbreviations

BArF4:

Tetrakis(pentafluorophenyl)borate

B(sia)2:

Diisoamylborane

BBN:

9-Borabicyclo[3.3.1]nonyl

BnOH:

Benzyl alcohol

BPin:

4,4,5,5-Tetramethyl-1,2,2-dioxoboryl

COD:

1,5-Cyclooctadiene

Cp*:

Pentamethylcyclopentadienyl

DME:

Dimethoxyethane

FA:

Formic acid

KC8:

Potassium graphite

kPa:

Kilopascal

MOM:

Methoxymethyl

NHC:

N-heterocyclic carbenes

RNA:

Ribonucleic acid

RT:

Room temperature

TOF:

Turnover frequency

TON:

Turnover number

TS:

Transition state

Ts:

Toluenesulfonyl

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Acknowledgments

This research was supported by GIF (German-Israeli Foundation for research and development) Grant N I-1508-302.5/2019. This work was supported by the RUDN University Program “5-100.” We are grateful for all stimulating discussion with many colleagues and friends and in particular for all work and insights provided by current and past group members.

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Authors and Affiliations

  1. Institute of Chemistry, The Hebrew University, Jerusalem, Israel

    Ajeet Singh & Dmitri Gelman

  2. Institute of Inorganic Chemistry, Faculty of Chemistry and Mineralogy, Leipzig University, Leipzig, Germany

    Evamarie Hey-Hawkins

  3. Peoples’ Friendship University of Russia (RUDN University), Moscow, Russia

    Dmitri Gelman

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  1. Ajeet Singh
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  2. Evamarie Hey-Hawkins
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  3. Dmitri Gelman
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Correspondence to Evamarie Hey-Hawkins or Dmitri Gelman .

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Editors and Affiliations

  1. Organic Chemistry & Catalysis, Utrecht University, Utrecht, The Netherlands

    Gerard van Koten

  2. Institute of Applied Synthetic Chemistry, Vienna University of Technology, Vienna, Austria

    Karl Kirchner

  3. Organic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, The Netherlands

    Marc-Etienne Moret

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Singh, A., Hey-Hawkins, E., Gelman, D. (2020). Cooperative Reactivity by Pincer-Type Complexes Possessing Secondary Coordination Sphere. In: van Koten, G., Kirchner, K., Moret, ME. (eds) Metal-Ligand Co-operativity. Topics in Organometallic Chemistry, vol 68. Springer, Cham. https://doi.org/10.1007/3418_2020_65

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