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Transition Metal Complexes for Hydrogen Activation

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Nanostructured Materials for Next-Generation Energy Storage and Conversion

Abstract

Hydrogen activation is a very important industrial process for hydrogenation reactions and ammonia production. The hydrogen splitting and hydride transfer process can be classified as homolytic and heterolytic cleavage of molecular hydrogen on mono- and multinuclear transition metal centers. Hydrogenase enzymes have inspired researchers in the field of organometallic chemistry to develop small molecule structural models of active sites and thus to mimic the biological system to activate molecular hydrogen. Multinuclear cluster complexes, including those containing heavy main group metals, can bind hydrogen molecule under mild conditions in a reversible fashion. This chapter aims at providing introductory review to cover various types of transition metal complexes that can split molecular hydrogen. The interaction between hydrogen molecule and metal centers, which determines the distance between two hydrogen atoms, will affect hydrogen splitting. The mechanism of such interactions will be discussed in details. Hydrogenation reactions catalyzed by transition metal complexes or heterogeneous nanocatalysts derived from metal cluster complexes will also be introduced.

Author Contribution

The chapter context was mainly compiled by Dr. Y. Kan under the supervision of Dr. Q. Zhang. The introduction part, chemical expression, and the revision of other subsections were examined and corrected by Dr. J. Liu and Dr. S. Bashir.

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Abbreviations

BArF :

[B{C6H3(CF3)2}4

Bn:

Benzyl

bq:

7,8-Benzoquinolato

CDA:

Cyclododecane

CDE:

Cyclododecene

CDT:

Cyclododecatriene

COD:

1,5-Cyclooctadiene

Cp:

η5-Cyclopentadienyl

Cy:

Cyclohexyl

DFT:

Density functional theory

depe:

1,2-bis(diethylphosphino)ethane

dppe:

1,2-bis(diphenylphosphino)ethane

EAC:

Ethyl (Z)-1-acetamidocinnamate

EPR:

Electron paramagnetic resonance

EXAFS:

Extended X-ray absorption fine structure

Fc:

Ferrocene

NMR:

Nuclear magnetic resonance

PCy3 :

Tricyclohexylphosphine ligand

PiPr3 :

Triisopropylphosphine ligand

PR2 :

Phosphido ligand

PR3 :

Phosphine ligand

Py:

Pyridine

ROP:

Ring opening polymerization

TOF:

Turnover Frequency

Tp:

Trispyrazolylborate

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Acknowledgement

The technical support from the Departments of Chemistry at Texas A&M University and Washington State University were duly acknowledged.

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Authors and Affiliations

  1. Department of Chemistry, Texas A&M University, College Station, TX, USA

    Yuwei Kan

  2. Department of Chemistry, Washington State University, Pullman, WA, USA

    Yuwei Kan & Qiang Zhang

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  1. Yuwei Kan
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Correspondence to Qiang Zhang .

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  1. Department of Chemistry, Texas A&M University, College Station, TX, USA

    Ying-Pin Chen

  2. Department of Chemistry, Texas A&M University–Kingsville, Kingsville, TX, USA

    Sajid Bashir

  3. Department of Chemistry, Texas A&M University–Kingsville, Kingsville, TX, USA

    Jingbo Louise Liu

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Kan, Y., Zhang, Q. (2017). Transition Metal Complexes for Hydrogen Activation. In: Chen, YP., Bashir, S., Liu, J.L. (eds) Nanostructured Materials for Next-Generation Energy Storage and Conversion. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-53514-1_2

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