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The Chemical Bond III pp 63–77Cite as

Sigma Bonds as Ligand Donor Groups in Transition Metal Complexes

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Part of the book series: Structure and Bonding ((STRUCTURE,volume 171))

Abstract

Covalent X–H bonds, particularly where X is H, C, B, and Si, can act as Lewis base ligands in forming metal complexes of general type L n M(H–X), where the M–H–X angle is strongly bent so that the coordination can best be considered as side-on. The binding is greatly enhanced by back donation from the metal into the X–H σ* orbital. This elongates and eventually breaks the X–H bond, leading to characteristic structural, physicochemical characteristics and alteration of the reactivity of the ligand. The requirement for back donation means that the appropriate L n M fragment must usually have appreciable π donor character. Since the binding of the X–H bond to the metal center is relatively weak, and the binding of the deprotonated X− group left behind is much stronger, the binding also facilitates proton loss from the X–H bond. This electron redistribution results in reactivity differences which may be exploited. The case of H2 is treated in most detail in this review, because of its central place in the field.

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Abbreviations

2e,3c:

Two-electron three-center bonding

CD:

Chatt–Dewar (bonding model)

Cy:

Cyclohexyl

dppe:

Ph2PCH2CH2PPh2

dppp:

Ph2PCH2CH2CH2PPh2

MCP:

Metalacyclopropane (bonding model)

pz:

Pyrazolyl

T 1 :

Spin–lattice relaxation time (in NMR spectroscopy)

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Author information

Authors and Affiliations

  1. Department of Chemistry, Yale University, 225 Prospect Street, New Haven, CT, 06520-8107, USA

    Robert H. Crabtree

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  1. Robert H. Crabtree
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Correspondence to Robert H. Crabtree .

Editor information

Editors and Affiliations

  1. Inorganic Chemistry Laboratory, University of Oxford Inorganic Chemistry Laboratory, Oxford, United Kingdom

    D. Michael P. Mingos

Additional information

Dedicated to Greg Kubas in recognition of his foundational contributions to the field

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Crabtree, R.H. (2015). Sigma Bonds as Ligand Donor Groups in Transition Metal Complexes. In: Mingos, D. (eds) The Chemical Bond III. Structure and Bonding, vol 171. Springer, Cham. https://doi.org/10.1007/430_2015_175

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