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The Catalytic Binuclear Elimination Reaction: Importance of Non-linear Kinetic Effects and Increased Synthetic Efficiency

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Homo- and Heterobimetallic Complexes in Catalysis

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 59))

Abstract

In the context of metal-mediated organic synthesis, cooperativity and synergism are rather broad terms which are often used to denote systems where unusual rate or selectivity effects are observed. These effects can be exhibited by monometallic, heterobimetallic and even multimetallic systems. The present contribution looks exclusively at one of the simplest cases, namely, systems possessing simultaneously both mononuclear and dinuclear complexes (hence both monometallic and heterobimetallic are included, but multimetallic systems are excluded). In Sect. 1, a brief introduction to the general area and a working definition for catalytic binuclear elimination reaction (CBER) is provided. In Sect. 2, we step back and classify the broad range of systems under consideration in order to enumerate the host of reaction networks considered, the potential for non-linear kinetic effects and how this relates to concepts of synthetic efficiency. In Sect. 3, we return to specific examples of CBER, how they fit into the overall context of the systems classification and how they can be identified in an unambiguous manner using in situ spectroscopic techniques. Indeed, tests can be constructed which permit the experimentalist to check crucial features and characteristics consistent with CBER. The present contribution focuses on the subarea in which CBER systems exist and hence CBER’s scope for organic syntheses.

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Notes

  1. 1.

    The rate r has taken a product-centric perspective throughout. However, there are many levels of interpretation, and they serve different purposes. Taking a metal-centric perspective, the rate relationships take the form (1) M r 1 = 1/2 M r 2 and (2) M r 3 = (1/2)M r 2 + M r 4.

  2. 2.

    Taking a metal-centric perspective, the rate relationships take the form (1) M r 1 = M r 2 and (2) M′ r 3 = M′ r 2 + M′ r 4.

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Acknowledgement

The author would like to thank the Agency for Science Technology and Research for generous support of this research. The author would also like to thank Dr Marco Klähn for his recent and extensive computational work concerning CBER and allowing the inclusion of Fig.22.

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  1. Institute of Chemical and Engineering Sciences (ICES), Agency for Science Technology and Research (A*STAR), 1 Pesek Rd, Jurong Island, 627833, Singapore

    Marc Garland

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  1. Equipe C "Catalyse et Chimie Fine", Laboratoire de Chimie de Coordination du CNRS, Toulouse Cedex, France

    Philippe Kalck

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Garland, M. (2015). The Catalytic Binuclear Elimination Reaction: Importance of Non-linear Kinetic Effects and Increased Synthetic Efficiency. In: Kalck, P. (eds) Homo- and Heterobimetallic Complexes in Catalysis. Topics in Organometallic Chemistry, vol 59. Springer, Cham. https://doi.org/10.1007/3418_2015_151

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