The Organometallic Chemistry of the Transition Metals

Robert H. Crabtree

• Publisher: Wiley
• Year: 2019
• ISBN:
  9781119465867
• Edition: 7
• Topic: Physical Sciences
• Subtopic: Organic Chemistry

Provides vital information on organometallic compounds, their preparation, and use in synthesis, and explores the fundamentals of the field and its modern applications

Fully updated and expanded to reflect recent advances, the new, seventh edition of this bestselling text presents students and professional chemists with a comprehensive introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction mechanisms and detailed descriptions of contemporary applications. Increased focus is given to organic synthesis applications, nanoparticle science, and green chemistry. This edition features up-to-date examples of fundamental reaction steps and greater emphasis on key topics like oxidation catalysis, CH functionalization, nanoclusters and nanoparticles, and green chemistry. New coverage is added for computational chemistry, energy production, and biochemical aspects of organometallic chemistry.

The Organometallic Chemistry of the Transition Metals, Seventh Edition provides new/enhanced chapter coverage of ligand-assisted additions and eliminations; proton-coupled electron transfer; surface, supported, and cooperative catalysis; green, energy, and materials applications; and photoredox catalysis. It covers coordination chemistry; alkyls and hydrides; Pi-complexes; and oxidative addition and reductive elimination. The book also features sections on insertion and elimination; spectroscopy; metathesis polymerization and bond activation; and more.

• Provides an excellent foundation of the fundamentals of organometallic chemistry
• Includes end-of-chapter problems and their solutions
• Expands and includes up-to-date examples of fundamental reaction steps and focuses on important topics such as oxidation catalysis, CH functionalization, nanoparticles, and green chemistry
• Features all new coverage for computational chemistry, energy production, and biochemical aspects of organometallic chemistry

The Organometallic Chemistry of the Transition Metals, Seventh Edition is an insightful book that will appeal to all advanced undergraduate and graduate students in organic chemistry, organometallic chemistry, inorganic chemistry, and bioinorganic chemistry, as well as any practicing chemist in those fields.

1
Introduction

Organometallic chemistry fills in a gap and makes a conceptual link between organic and inorganic chemistry in its focus on the binding of organic fragments to metals via one or more M-C bonds. The metals can come from the main group, in the s and p blocks of the periodic table, as in the Grignard reagent, CH₃MgBr, or from the transition elements of the d and f blocks, as in the ethylene complex salt, K[(C₂H₄)PtCl₃]. Main‐group organometallics, such as n‐BuLi and PhB(OH)₂, have proved so useful for organic synthesis that they are extensively covered in organic chemistry courses and textbooks. Here, we look instead at the transition metals where the intervention of metal d and f orbitals opens reaction pathways not otherwise accessible. While main‐group organometallic reagents are typically stoichiometric – used in a simple mole ratio with the reactant – many transition metal organometallics are now most often seen as catalysts, where the metal‐to‐reactant ratio is typically 1 : 100 but can be 1 : 10⁶ or even beyond. The higher the ratio, the greater the practicality of an organometallic catalyst, even if expensive.

1.1 Why Study Organometallic Chemistry?

The expanding range of applications of transition metal catalysis in organic chemistry helped explain the rise of d block organometallics from the late twentieth century. As late as 1975, the great majority of organic syntheses had no recourse to transition metals at any stage; in contrast, they now almost always appear, often as catalysts. Catalysis is also a central principle of the twenty‐first century field of green or sustainable chemistry[1] because it helps avoid the waste formation in chemical processes, for example, of Mg salts from Grignard reactions, and its high selectivity minimizes the need for product separations.

In 2012, the noted organic chemist and Associate Editor of the Journal of Organic Chemistry, Carsten Bolm[2], published a ringing endorsement of organometallic methods as applied to organic synthesis:

In 1989, OMCOS‐VI [the 6^th International Conference on Organometallic Chemistry Directed Toward Organic Synthesis] took place in Florence and … left me with the impression that all important transformations could – now or in the future – be performed with the aid of adequately fine‐tuned metal catalysts. Today, it is safe to say that those early findings were key discoveries for a conceptual revolution that occurred in organic chemistry in recent years. Metal catalysts can be found everywhere, and many synthetic advances are directly linked to … developments in catalytic chemistry.

Organometallics have a much longer history in industrial chemistry. In the 1880s, Ludwig Mond refined crude nickel in a stream of hot CO to volatilize the Ni as Ni(CO)₄; subsequent stronger heating then deposited pure Ni. From the 1930s, the Co₂(CO)₈ catalyzed hydroformylation of 1‐ or 2‐butene with H₂ and CO was applied to n‐pentanal and n‐pentanol manufacture. From the 1970s right up to today, a variety of homochiral pharmaceuticals have been produced by asymmetric catalysis, in which racemic reagents are transformed into single pure product enantiomers. Other examples include alkene polymerization to give polyethylene and polypropylene, hydrocyanation of butadiene for nylon manufacture, acetic acid synthesis from MeOH and CO, and hydrosilylation to produce silicone materials.

We are beginning to see applications elsewhere. From 2001, Cu catalyzed “click” chemistry has allowed coupling molecular units even within living cells or in advanced materials[3]. Some of the organic light‐emitting diodes (OLEDs) in cell phone displays rely on organometallics. Samsung has produced OLED screens since 2008 that use a cyclometallated Ir complex as the red emitter. They are also useful in solid‐state light‐emitting electrochemical cells (LECs)[4]. Photoredox catalysis (Section 14.9) is a rising field in organic synthesis in which a favored photosensitizer is an organometallic iridium complex resemb...