Polar Organometallic Reagents: Synthesis, Structure, Properties and Applications

This volume will provide detailed information on fundamental, structural and theoretical aspects of polar organometallic reagents, with a particular focus on synergic heterometallic bases, recent advances in characterisation techniques, and synthetic applications. The book will, for the first time, collect together both structural and synthetic achievements that have taken place in the rapidly developing area of synergic reagents, collating new synthetic work with our improved mechanistic understanding of heterobimetallic complexes. Following an introductory chapter, the book will go on to discuss the following topics:

• Alkali metal synergic bases in the solid state: The development of synergic bases will be covered. This has happened since 1999 and involves the integration of two metals - one generally an alkali metal - in a single organometallic. Early developments in the field will be discussed as will the logic behind their creation. The structural ambiguities presented by these complexes will be considered as will evidence for competition between co-operativity between monometallic bases and the action of bimetallic bases.
• Alkali earth organometallics: "Turbo Grignard" reagents: Recent advances in Grignard chemistry will be documented. These have mostly taken the form of so-called "Turbo Grignard" reagents. These are achieved by integrating Grignard reagents with alkali metal salts and have achieved unprecedented reactions and improved performance.
• Theoretical studies: Historically theoretical work has played a crucial part in elucidating the structure and bonding displayed by polar organometallics. More recently major advances have been made in the use of calculations to plot reaction pathways/mechanisms and elucidate the interconversion of species in solution in response to the introduction of substrates.

• Solution structures and understanding reactivity: DOSY, synergic bases and metal cooperativity: The development of 2D methods for the interrogation of particle size in solution has had an enormous impact on our ability to assess solution structural chemistry and its impact on reaction mechanism. The highest profile development in this field has been in the technique DOSY. The application of DOSY to heterobimetallics has begun to appear in the literature over the last 2-3 years.
• New selectivity and polymetalation in organic synthesis with polar organometallics: The advent of new reaction and regio-/stereo-/chemoselectivities will be discussed.
• Applications in organic synthesis
• Environmental efforts: Early efforts at developing greener applications of polar organometallics will be reported on, including the development of catalytic main group chemistry based on at least one component of synergic system, the use of non-traditional reaction environments, the search for enhanced atom efficiency and reactions at room temperature