How far have we come?

Robert H. Crabtree*
Yale Chemistry Department and Energy Sciences Institute, 225 Prospect St., New Haven, CT 06520-8107, USA. E-mail:

Fred Basolo (1907–2007), one of the pioneers of mechanistic inorganic chemistry, used to tell a tale that illustrated the state of the field at the outset of his independent career. At an international conference in the late 1940s or early 1950s, he heard Walter Hieber (1895–1976), the founder of metal carbonyl hydride chemistry, describe his recent work on a number of carbonyl substitution reactions. At the end of the talk, Basolo asked Hieber “How do these substitutions go?” The answer was swift: “I do not engage in chemical philosophy.” Whether true or not—and there is no way to be sure at this remove—this vignette does authentically reflect the state of inorganic chemistry in the very early postwar years. It was not unusual at this time to encounter major chemistry departments that had no acknowledged inorganic chemists at all on the faculty. Only with the advances of the 1950s, such as Taube's work on electron transfer, did chemists in other fields become aware of an emerging renaissance in the field, based on mechanistic thinking.

The mechanistic studies carried out by pioneers such as Basolo, Gray and Taube not only gave us the starting point for future work but led to an increased respect for inorganic chemistry by chemists in general. The hopes of the mechanists that reaction design based on mechanistic principles would soon become universal have perhaps been only partially fulfilled, but the hope is now at least part of most grant proposals.

The spectacular advance of computer technology and theoretical chemistry has enabled one of the most important changes in mechanistic studies. At one time purely experimental, mechanistic studies now routinely include computational work. In the best examples of such work, the experimental and computational parts hold a dialogue in which each advance on one side suggests a modified approach on the other, going back and forth until a satisfactory answer is achieved.

This themed issue celebrates the achievements of the field by highlighting some of the best recent developments from the Dalton Transactions authorship. I hope the articles will stimulate the Dalton Transactions readership to apply similar methods to their own special problems.

This journal is © The Royal Society of Chemistry 2013