Top Organomet Chem (2016) 59: 187–232
DOI: 10.1007/3418_2015_151
# Springer International Publishing Switzerland 2015
Published online: 17 December 2015
The Catalytic Binuclear Elimination
Reaction: Importance of Non-linear Kinetic
Effects and Increased Synthetic Efficiency
Marc Garland
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.
Keywords Catalytic binuclear elimination reaction (CBER), Hydroformylation,
In-situ spectroscopy, Rhodium
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
1.1 Catalytic Syntheses, Cooperativity and Synergism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
1.2 Stoichiometric Binuclear Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
M. Garland (*)
Institute of Chemical and Engineering Sciences (ICES), Agency for Science Technology and
Research (A*STAR), 1 Pesek Rd, Jurong Island 627833, Singapore
e-mail: marc_garland@ices.a-star.edu.sg
DOI: 10.1007/3418_2015_151
# Springer International Publishing Switzerland 2015
Published online: 17 December 2015
The Catalytic Binuclear Elimination
Reaction: Importance of Non-linear Kinetic
Effects and Increased Synthetic Efficiency
Marc Garland
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.
Keywords Catalytic binuclear elimination reaction (CBER), Hydroformylation,
In-situ spectroscopy, Rhodium
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
1.1 Catalytic Syntheses, Cooperativity and Synergism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
1.2 Stoichiometric Binuclear Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
M. Garland (*)
Institute of Chemical and Engineering Sciences (ICES), Agency for Science Technology and
Research (A*STAR), 1 Pesek Rd, Jurong Island 627833, Singapore
e-mail: marc_garland@ices.a-star.edu.sg