Homogeneous organometallic catalysis

In the near future, it is believed that a major part of macromolecular chemistry will receive a strong impact from homogeneous organometallic catalysis. Thus, poly-coupling reactions with redox-sensitive precursor compounds to give polymers like 38 were discovered [72]. 

J. A. Loch, R. H. Crabtree, Rapid screening and combinatorial methods in homogeneous organometallic catalysis, PureAppl. Chem., 2001, 73(1) 119-128. 

Sperger, T. Sanhuesa, I. A. Kalvet, L Schoenebeck, F. Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh An Overview of Commonly Employed DPT Methods and Mechanistic Insights. Chem. Rev. 2015,115,0532-9586. 

In the simplest form of aqueous organometallic catalysis (AOC) the reaction takes place in a homogeneous aqueous solution. This requires all... 

Research into homogeneous hydrogenation and its applications prior to 1973 are comprehensively described in the now classic book of James [3]. More recent books on hydrogenation [1] and on aqueous organometallic catalysis [2] contain special chapters on hydrogenation reactions in water. In adition, all reviews on aqueous organometalhc catalysis devote considerable space to this topic, see e.g. references [9-12]. 

Scheme 12.1 Interplay of homogeneous and heterogeneous organometallic catalysis.

Organometallic catalysis in biphasic aqueous/organic media is a novel and environmentally benign approach to combining the inherent advantages of homogeneous catalysts (high activity and selectivity) with the ease of separation... 

The best solvent is no solvent and if a solvent (diluent) is needed then water is preferred [100]. Water is non-toxic, non-inflammable, abundantly available and inexpensive. Moreover, owing to its highly polar character one can expect novel reactivities and selectivities for organometallic catalysis in water. Furthermore, this provides an opportunity to overcome a serious shortcoming of homogeneous catalysts, namely the cumbersome recovery and recycling of the catalyst. Thus, performing the reaction in an aqueous biphasic system, whereby the... 

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