The bumpy road to sustainability: Reassessing the history of the twelve principles of green chemistry.

The widely recognized 12 principles of green chemistry, introduced in 1998, have become a focal point for environmentally conscious chemists worldwide. These principles are regarded as a comprehensive summary of the achievements of green chemistry and a roadmap for future advancements in the field, aligning chemistry with sustainability goals. They have been hailed as groundbreaking in addressing pressing global challenges, including environmental and climate crises. However, a closer examination reveals a more nuanced perspective. Criticisms have emerged, asserting that these principles may stifle the creativity of emerging chemists and distort the history of green chemistry. Dissenting voices are growing, prompting scholars to reevaluate their effectiveness and relevance. It appears that the 12 principles provide an overarching narrative and a common language to practitioners of green chemistry but their success does not proceed from their 'scientific' qualities but should be rather understood in socio-historical terms. Analysing these principles provides insights into the mindset and collective identities of chemists, highlighting how underlying value-driven frameworks shape scientific discourse. It becomes evident that these frameworks can be co-opted and persist unquestioned for extended periods. The objective of this article is to demystify the 12 principles, stimulating dialogue on the necessity of self-reflection within scientific fields that heavily rely on value-laden sustainability-oriented terminology.

Beyond green chemistry: Radical environmental transformation through Sanfte Chemie (1985-1995).

Sanfte Chemie was a concept formulated in the 1980s in Germany by a group of environmentally conscious scholars. It emerged within a unique environment, marked by its radical critique of dominant forms of rationality, and against the rich background of German philosophical technocritical traditions. Its purpose was to profoundly reshape the practice of chemistry and the organization of the chemical industry along the lines of sustainability. In contrast to later concepts like green or sustainable chemistry, Sanfte Chemie went beyond setting new research directions; it critically reevaluated the entire epistemological foundation upon which the science of chemistry was built. Under the auspices of the German Green Party, the concept flourished in the 1980s before falling out of grace in the following decade. While largely deemed overly radical in its time and then subsequently forgotten, Sanfte Chemie not only anticipated some of the most promising trends in sustainability science today but also offered unique insights that may shed new light on the challenges of the ongoing environmental crisis.

The Uncertain Role of Nominations for the Nobel Prize in Chemistry†.

The solicitation of nominations for the Nobel Prizes in Chemistry (NPch) is and has been the first step in the selection process since the very first awards were made in 1901. The number of nominations solicited by and provided to the Nobel Committee for Chemistry supports the belief by the nominators that their nominations are meaningful. In this publication, we examine data culled from the Nobel Prize Nomination Archives for the period 1901-1970 of the variable role of nominations in the selection process for the Nobel Prize in Chemistry. The evidence is overwhelming that nominations, in general, during the 1901-1970 period have not been the deciding, overriding factor in the selection of the recipients of the NPch. Rather, we posit that nominations from the preselected nominator-pool have been a source of information for the Committee, used to suggest future years' contenders and possibly served as motivation for the Committee to seek nominations for specific nominees for future years. It is also clear that selections are often influenced by personal prejudices, for example, friendships, rivalries, and nationality.

Introduction to "The Woodward-Hoffmann Rules. From May 5, 1964, to November 30, 1964".

An introduction is provided to Publication 11 in the series of articles by the author on the history of the Woodward-Hoffmann (W-H) rules. Now permanently open access (CC-BY) at http://pubs.acs.org/doi/abs/10.1021/acs.joc.5b01792, Paper 11 was published in 2015 in The Journal of Organic Chemistry to celebrate the 50th anniversary of the W-H rules. This paper summarizes the content of Publications 1-10 in the series and provides an idea of the major components of Publication 11.

Why Woodward and Hoffmann? And Why 1965?

Previous publications in this series on the history of the development of the Woodward-Hoffmann rules revealed why Woodward and Hoffmann were prime candidates to solve the pericyclic no-mechanism problem. This publication explains why it was the collaborative team of R. B. Woodward and Roald Hoffmann who did solve this mechanistic problem in a series of five communications in the Journal of the American Chemical Society in 1965. That is, the reasons why Woodward and Hoffmann were the perfect team, and why their individual capabilities, experiences, and qualities provided the perfect synergy are described. In part, this was the right time and the right place for them both, but the synergies were fundamental, intrinsic and idiosyncratic as a collaborative pair. Their orbital symmetry rules provided the mechanism of all concerted pericyclic reactions including electrocyclizations, cycloadditions, and sigmatropic rearrangements. Why it was 1965 and not earlier is also discussed.

Reinventing the wheel: A critical look at one-world and circular chemistries.

With the rise of environmental awareness among chemists, more and more programmatic frameworks try to guide chemists to conduct research in an ethical manner. While green chemistry remains the most popular and influential of these concepts, not all scholars choose to embrace it. One world chemistry and circular chemistry are examples of this new trend. They constitute an attempt to profoundly reshape the practice of chemistry along new lines to make the discipline more relevant to the changing social, environmental and economic reality. And yet, both concepts betray a lack of familiarity with the recent history of chemistry and of sustainability undermining their overall message. The article indicates that the history of chemistry can play a crucial role in enriching the conversation on the direction chemistry should take towards the socio-environmental transition.

The Many Chemists Who Could Have Proposed the Woodward-Hoffmann Rules (Including Roald Hoffmann) But Didn't: The Theoretical and Physical Chemists†.

It is a reasonable question to ask, why, as of 1965 when the five Woodward-Hoffmann communication appeared, did no other physical chemist or chemical physicist or theoretical chemist discover the orbital symmetry rules for all pericyclic reactions? Two theoretical chemists - Luitzen Oosterhoff (in 1961) and Kenichi Fukui (in 1964) had discovered portions of the orbital symmetry rules; their stories appear in the papers immediately preceding this paper which is Paper 5 in a 27-paper series on the history of Woodward-Hoffmann rules. Concise yet telling stories of 19 other chemists who could have, might have, perhaps even should have discovered the Woodward-Hoffmann rules are presented with explanations as to why they did not do so. Social, political, and scientific explanations will summarize the analyses.

Icilio Guareschi and his amazing "1897 reaction".

Organic chemistry honors Icilio Guareschi (1847-1918) with three eponymic reactions, the best known ones being the Guareschi synthesis of pyridones and the Guareschi-Lustgarten reaction. A third Guareschi reaction, the so-called "Guareschi 1897 reaction", is one of the most unusual reactions in organic chemistry, involving the radical-mediated paradoxical aerobic generation of hydrocarbons in near-neutral water solution. A discussion of the mechanism of this amazing reaction, the only metal-free process that generates hydrocarbons, and the implications of the approach in biology and geosciences mirrors the multifaceted scientific personality of the discoverer. Thus, Guareschi's eclectic range of activities spans a surprising variety of topics, overcoming the boundaries of the traditional partition of chemistry into organic, inorganic, and analytical branches and systematically crosses the divide between pure and applied science as well as between the history of chemistry and the personal contributions to its development.

A Homage to Siegfried Hünig and His Research.

Examples from different research areas of Siegfried Hünig are displayed to remind us that organic chemistry owes much more than Hünig's base to this exceptionally versatile and creative chemist. The main research lines dealing with the synthesis and physical characterization of new dyes, multistage redox systems, and organic metals will be presented as well as his contributions to enamine chemistry, the discovery of diimine as a hydrogenation agent, and nucleophilic acylation with trimethylsilyl cyanide, which are less well-known nowadays. In addition, exotic compounds with parallel C=C and N=N bonds were systematically studied in Hünig's group. Reflecting on the development of his research demonstrates both the importance of a systematic approach and how fruitful entirely unexpected results are if they meet a "well-prepared mind". During Hünig's academic career, teaching played an indisputable role. His efforts in modernizing the chemistry institute at Würzburg and his support of young researchers in the academic system in Germany are also highlighted.

Permanganyl Fluoride: A Brief History of the Molecule MnO3 F and of Those Who Cared For It.

Permanganyl fluoride's existence at the stability threshold in the series of oxides and oxide fluorides of the late 3d transition metals is reflected by its experimentally challenging properties and by the difficulties posed in the theoretical description of its bonding characteristics. The history of this molecule is reviewed from early qualitative observations and the growing scattered information on its chemical and physical properties to the accurate determination and interpretation of its molecular structure and spectral features. The still problematic theoretical models for MnO4 - and MnO3 F are briefly presented in the broader context of the chemistry of elements in high oxidation states. Short biographies of the scientists engaged in these studies are offered. Related technetium and rhenium compounds are briefly considered for comparison.

The Relationship of William Henry Perkin, Jr. and Sir Robert Robinson: Teacher and Student, then Student and Teacher.

William Henry Perkin, Jr. FRS, the son of the inventor of mauve and other commercial dyes and credited for initiating the industrialization of chemistry, was himself a notable chemist. He was the Professor of Organic Chemistry at Manchester from 1892-1912 and then was the Waynflete Professor of Chemistry at Oxford and the first Head of the Dyson Perrins Laboratory from 1912-1929. One of Perkin's graduate students and research assistants at Manchester was Robert Robinson, subsequently Sir Robert Robinson, FRS and recipient of the 1947 Nobel Prize in Chemistry. Perkin and Robinson had perhaps the most productive and broad collaboration between a professor and one's student. Together, during and after Robinson's student days, they had 71 joint publications, 25 of which involved just the two of them, 17 of which involved the structure determination of strychnine, and eight of which were published after Perkin's death in 1929. Upon Perkin's early death, Robinson succeeded him as the fourth Waynflete Professor of Chemistry at the Dyson Perrins Laboratory, Oxford University. This Essay will examine the professional relationship of Perkin, Jr. and Robinson as revealed in their joint publications on the structure of strychnine.

Primo Levi: A frustrated stereochemist?-Insight in hindsight.

Primo Levi (1919-1987) has become an iconic figure at the intersection of chemistry and culture. Levi has long been praised for his autobiographical account as survivor in Auschwitz and by his literary masterpiece "The Periodic Table." Little is however known beyond such facts, especially his academic period and early research on stereochemistry at the University of Turin, which were abruptly truncated by the racial laws and WWII. Even if, later on, Primo Levi succeeded as industrial chemist, he had a vivid interest in molecular asymmetry that lasted through his entire life. This concise paper highlights a little known academic period in the midst of social and political upheaval. Levi left us his humanity in an otherwise tortuous life, and his literature took inspiration from chemistry; perhaps as a metaphor connecting the physical world and people's life.

Nikolay Zelinsky (1861-1953): Mendeleev's Protege, a Brilliant Scientist, and the Top Soviet Chemist of the Stalin Era.

This Essay outlines the life path and scientific achievements of Nikolai Zelinsky to testify to his contributions to organic chemistry, catalysis, and petrochemistry. His legacy includes four name reactions (the Hell-Volhard-Zelinsky reaction, 1887; the Zelinsky-Stadnikov reaction, 1906; Zelinsky irreversible catalysis, 1911; the Zelinsky-Kazansky acetylene trimerization, 1924), pioneering contributions to the main oil-refining processes (thermal cracking, catalytic cracking, hydrodesulfurization, reforming, and oxidative regeneration of coked catalysts), the coal gas mask, Pd/C and other supported catalysts, and a very large scientific school.

Recent attempts to change the periodic table.

The article concerns various proposals that have been made with the aim of improving the currently standard 18-column periodic table. We begin with a review of 8-, 18- and 32-column formats of the periodic table. This is followed by an examination of a possible, although rather impractical, 50-column table and how it could be used to consider the changes to the periodic table that have been predicted by Pyykkö in the domain of superheavy elements. Other topics reviewed include attempts to derive the Madelung rule as well as an analysis of what this rule actually provides. Finally, the notion of an 'optimal' periodic table is discussed in the context of recent work by philosophers of science who have examined the nature of classifications in general, as well as the notion of natural kinds. The article takes an unapologetically philosophical approach rather than focusing on specific data concerning the elements. Nevertheless, some pragmatic issues and educational aspects of the periodic table are also examined. This article is part of the theme issue 'Mendeleev and the periodic table'.

Rolf Huisgen's Classic Studies of Cyclic Triene Diels-Alder Reactions Elaborated by Modern Computational Analysis.

Rolf Huisgen explored the Diels-Alder reactions of 1,3,5-cycloheptatriene (CHT) and cyclooctatetraene (COT) with the dienophiles maleic anhydride and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) to determine the kinetics and mechanisms of various electrocyclizations and Diels-Alder reactions. These reactions have been examined with density functional theory. Modern computational chemistry has provided information not previously available by experiment. Transition states for all the reactions have been identified, and their Gibbs energies are used to explain the experimental reactivities. Zwitterionic intermediates were not found in the [4+2] cycloadditions of both CHT or COT with PTAD and are thus not involved in these reactions. [2+2+2] cycloadditions, as an alternative path to the Diels-Alder products, are highly disfavored. Rapid double nitrogen inversion was found for the cycloaddition products with PTAD.

Chemistry and slavery in the Scottish Enlightenment.

The Scottish Enlightenment has long been identified with abolitionism because of the writings of the moral and economic philosophers and the absence of slaves in Scotland itself. However, Scots were disproportionately represented in the ownership, management, and especially medical treatment of slaves in the British Caribbean. Sugar and cotton flowed into Glasgow and young, educated Scots looking for work as traders, bookkeepers, doctors made the return trip back to the Caribbean to manage the plantations. Chemically trained doctors and agriculturalists tested their theories in the plantations and developed new theories based on their experimentation on the land and slaves. In foregrounding the participation of Scottish trained chemists in the practice of slavery, I argue that the development of eighteenth-century chemistry and the broader intellectual Enlightenment were inextricably entangled with the economic Improvement Movement and the colonial economy of the British slave trade.

Chemistry-An Editorial Journey.

The silver anniversary of Chemistry-A European Journal is a great reason to celebrate and a good opportunity for reflection. This Editorial looks back at the history of the journal through the eyes of the Editorials written by a variety of the key players and stakeholders.

Exploration of the chemical space and its three historical regimes.

Chemical research unveils the structure of chemical space, spanned by all chemical species, as documented in more than 200 y of scientific literature, now available in electronic databases. Very little is known, however, about the large-scale patterns of this exploration. Here we show, by analyzing millions of reactions stored in the Reaxys database, that chemists have reported new compounds in an exponential fashion from 1800 to 2015 with a stable 4.4% annual growth rate, in the long run neither affected by World Wars nor affected by the introduction of new theories. Contrary to general belief, synthesis has been the means to provide new compounds since the early 19th century, well before Wöhler's synthesis of urea. The exploration of chemical space has followed three statistically distinguishable regimes. The first one included uncertain year-to-year output of organic and inorganic compounds and ended about 1860, when structural theory gave way to a century of more regular and guided production, the organic regime. The current organometallic regime is the most regular one. Analyzing the details of the synthesis process, we found that chemists have had preferences in the selection of substrates and we identified the workings of such a selection. Regarding reaction products, the discovery of new compounds has been dominated by very few elemental compositions. We anticipate that the present work serves as a starting point for more sophisticated and detailed studies of the history of chemistry.

The Periodic-Table-A Universal Icon: Its Birth 150†Years Ago, and Its Popularization Through Literature Art and Music.

This Essay projects the spark of genius of Mendeleev, whose efforts led to the effective formulation of the periodic table, which has placed the entire world of chemical matter on a palm. The periodic table gave rise to a central paradigm, which did for chemistry what Newton had done for physics and Darwin for biology. Subsequently the Essay recounts the popularization of the Periodic Table through literature by Primo Levi, Oliver Sacks and others, and through music and art by composers and artists, such as Jerry Feldman, the King Crimson band, Tom Lehrer, and George Brecht, Blair Bradshaw, Eugènia Balcells, etc.

Mikhail Kucherov: "The Experiment Confirmed my Hypothesis".

Named reactions are key points in the development of chemistry. Any competent chemist easily identifies the reaction named after Wittig, or Grignard, Diels-Alder, or Friedel-Crafts, Michael, or Favorsky. But how much do we can say about scientist who discovered it? This Essay is devoted to the transition-metal-catalyzed hydration of acetylenic hydrocarbons discovered by Russian chemist Mikhail Kucherov. This reaction is one of the most straightforward methods for the synthesis of carbonyl compounds. With it, in industry for a long time acetaldehyde was essentially manufactured from accessible unsaturated raw material-acetylene. This reaction is one of the first steps in the establishment of homogenous metal complex catalysis in organic synthesis. Herein, we described the history of this discovery and the role of many scientists in the development of research in this field. We would also like to show the life of Russian scientists in the latter half of the 19th century.