Register      Login
Historical Records of Australian Science Historical Records of Australian Science Society
The history of science, pure and applied, in Australia, New Zealand and the southwest Pacific
RESEARCH ARTICLE (Open Access)

Practising organometallic chemistry in nineteenth century Australia: David Orme Masson and diethyl magnesium

Ian D. Rae https://orcid.org/0000-0002-7579-3717 A *
+ Author Affiliations
- Author Affiliations

A School of Chemistry, University of Melbourne, Melbourne, Vic. 3010, Australia.

* Correspondence to: idrae@unimelb.edu.au

Historical Records of Australian Science 33(2) 122-132 https://doi.org/10.1071/HR22001
Published: 7 June 2022

© 2022 The Author(s) (or their employer(s)). Published by CSIRO Publishing on behalf of the Australian Academy of Science. This is an open access article distributed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND)

Abstract

By the late 1880s, the existence of alkyl derivatives of metals such as zinc and mercury was well established but diethyl magnesium had been poorly characterised and obtaining proof of its existence was a reasonable aim for chemists. Professor David Orme Masson and his student, Norman Wilsmore, at the university in the British colonial capital, Melbourne, accepted the challenge despite their distance from northern hemisphere centres of chemical research. The ‘tyranny of distance’ was tempered by their access to chemical journals and textbooks and by Masson’s connections at the ‘centre’, notably with William Ramsay. Wilsmore repeated the earlier experiments and also used methods that had been successful with other metals, but was unable to prepare diethyl magnesium. Masson rationalised this failure on the basis of the element’s position in the periodic classification of the elements that Mendeleev and Lothar Meyer had published, and on magnesium’s position on the atomic volume curve of Meyer, and concluded that diethyl magnesium could not exist. The weakness of these arguments was revealed when, near-coincidentally with Masson’s and Wilsmore’s publication of the results of their experiments, Philippe Löhr, working in Meyer’s laboratory, published successful syntheses of several alkyl magnesium derivatives by methods that had been unsuccessful in Wilsmore’s hands. Masson’s heuristic use of Meyer’s curve was unusual, and a notable feature of his approach to chemistry.

Keywords: alkyl, atomic volume, Frankland, Lohr, Meyer, organometallic, Wilsmore.


References

Aitken, R. A., and Gil, M. P. (2019) The periodic table and other wallcharts in the teaching of chemistry in St Andrews, 1884–1919, Philosophical Transactions of the Royal Society of London A, 378, 1–17.

Anonymous (1891) Thomas Carnelley, Journal of the Chemical Society Transactions, 59, 455–61.

Apjohn, J. (1864) Manual of the Metalloids, London.

Blainey, G. (1966) The Tyranny of Distance: How Distance Shaped Australian History, Melbourne.

Buckton, G. B. (1858) VIII—On the isolation of the radical, mercuric methyl, Philosophical Transactions of the Royal Society of London, 148, 163–8.
VIII—On the isolation of the radical, mercuric methylCrossref | GoogleScholarGoogle Scholar |

Buckton, G. B. (1859) XXI—On the isolation of the organo-metals, mercuric, stannic and plumbic ethyls; and observations on some of the derivatives: second memoir, Philosophical Transactions of the Royal Society of London, 149, 417–35.
XXI—On the isolation of the organo-metals, mercuric, stannic and plumbic ethyls; and observations on some of the derivatives: second memoirCrossref | GoogleScholarGoogle Scholar |

Burrows, G. J., and Turner, E. E. (1920) A new type of compound containing arsenic, Journal of the Chemical Society, 117, 1373–83.
A new type of compound containing arsenicCrossref | GoogleScholarGoogle Scholar |

Cahours, A. (1860a) Untersuchungen über die metallhaltigen organischen Radicale: erster Thiel, Annalen der Chemie und Pharmacie, 114, 227–55.
Untersuchungen über die metallhaltigen organischen Radicale: erster ThielCrossref | GoogleScholarGoogle Scholar |

Cahours, A. (1860b) Recherches sur les Radicaux Organométalliques, Annales de Chimie et de Physique, 58, 5–82.

Cahours, A. (1862) Untersuchungen über die metallhaltigen organischen Radicale, Annalen der Chemie und Pharmacie, 122, 48–71.
Untersuchungen über die metallhaltigen organischen RadicaleCrossref | GoogleScholarGoogle Scholar |

Carnelley, T. (1884) I—The periodic law, as illustrated by certain physical properties of inorganic compounds, The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, 18, 1–22.
I—The periodic law, as illustrated by certain physical properties of inorganic compoundsCrossref | GoogleScholarGoogle Scholar |

Carnelley, T. (1885) XXVIII—The periodic law, as illustrated by certain physical properties of organic compounds: part 1: the alkyl compounds of the elements, The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, 20, 259–68.
XXVIII—The periodic law, as illustrated by certain physical properties of organic compounds: part 1: the alkyl compounds of the elementsCrossref | GoogleScholarGoogle Scholar |

Chambers, D. W. (1991) ‘Does distance tyrannize science?’, in International Science and National Scientific Identity, eds R. W. Home and S. G. Kohlstedt, Dordrecht, Boston, pp. 19–38.

Cole Jr, T. M. (1975) Early atomic speculations of Marc Antoine Gaudin: Avogadro’s hypothesis and the periodic system, Isis, 66, 334–360.
Early atomic speculations of Marc Antoine Gaudin: Avogadro’s hypothesis and the periodic systemCrossref | GoogleScholarGoogle Scholar |

De Garis, B. K. (1990) Wilsmore, Norman Thomas Mortimer (1868–1940), Australian Dictionary of Biography, 12, 517–518.

Edwards, G. N. (1865) Two cases of poisoning by mercuric methide, Saint Bartolomew’s Hospital Reports, i, 141–150.

Edwards, G. N. (1866) Note on the termination of the second case of poisoning by mercuric methide, Saint Bartolomew’s Hospital Reports, ii, 211–212.

Fleck, H. (1893) Ueber magnesium-Alkyle, Justus Liebig’s Annalen der Chemie, 276, 129–147.
Ueber magnesium-AlkyleCrossref | GoogleScholarGoogle Scholar |

Fournier, J. (2013) Auguste Cahours (1813–1891), Les densités de vapeur, les organométalliques et la valence, l’actualité chimique, No. 373, avril, 27–30.

Frankland, E. (1849) Ueber die Isolirung der organischen Radicale, Annalen der Chemie und Pharmacie, 71, 171–213.
Ueber die Isolirung der organischen RadicaleCrossref | GoogleScholarGoogle Scholar |

Frankland, E. (1850) On the isolation of the organic radicals, Journal of the Chemical Society, 2, 263–296.

Frankland, E. (1861) On organo-metallic bodies, Transactions of the Chemical Society, 13, 177–235.

Frankland, E., and Duppa, B. F. (1863) L—On a new method of producing the mercury compounds of the alcohol-radicles, Journal of the Chemical Society, 16, 415–425.
L—On a new method of producing the mercury compounds of the alcohol-radiclesCrossref | GoogleScholarGoogle Scholar |

Frankland, E., and Duppa, B. F. (1864) III—On a new method on a new method of preparing the zinc-compounds of the alcohol-radicles, Journal of the Chemical Society, 17, 29–36.
III—On a new method on a new method of preparing the zinc-compounds of the alcohol-radiclesCrossref | GoogleScholarGoogle Scholar |

Friedel, C., and Crafts, J. M. (1863) Sur quelques nouvelles Combinaisons organique du Silicium et sur le Poids atomique de cet élément, Comptes rendus hebdomadaires de l’Academie des Sciences, 56, 590–593.

Gilman, H., and Schulze, F. (1927a) CCCLIII—Beryllium Dialkyls, Journal of the Chemical Society, , 2663–2669.
CCCLIII—Beryllium DialkylsCrossref | GoogleScholarGoogle Scholar |

Gilman, H., and Schulze, F. (1927b) Magnesium diethyl and its reaction with acetyl chloride, Journal of the American Chemical Society, 49, 2328–2330..
Magnesium diethyl and its reaction with acetyl chlorideCrossref | GoogleScholarGoogle Scholar |

Girolami, G. S., and Mainz, V. V. (2019) Mendeleev, Meyer, and atomic volumes: an introduction to an English translation of Mendeleev’s 1869 article ‘On the atomic volume of simple bodies’, Bulletin for the History of Chemistry, 44, 100–108.

Gladstone, J. H., and Tribe, A. (1877) XX—Preparation of copper-zinc couples, Journal of the Chemical Society, 31, 561–570.
XX—Preparation of copper-zinc couplesCrossref | GoogleScholarGoogle Scholar |

Gladstone, J. H., and Tribe, A. (1879) LXII—On dry copper-zinc couples and analogous reagents, Journal of the Chemical Society, 35, 567–578.
LXII—On dry copper-zinc couples and analogous reagentsCrossref | GoogleScholarGoogle Scholar |

Grignard, V. (1912) ‘The use of organomagnesium compounds in preparative organic chemistry’, Nobel lecture, 11 December. Available at https://www.nobelprize.org/uploads/2018/06/grignard-lecture.pdf [viewed January 2021]

Hallwachs, W., and Schafarik, A. (1859) Ueber die Verbindungen der Erdmetalle mit organischen Radicalen, Justus Liebig’s Annalen der Chemie, 109, 206–209.
Ueber die Verbindungen der Erdmetalle mit organischen RadicalenCrossref | GoogleScholarGoogle Scholar |

Home, R. W. (1991) ‘A world-wide scientific network and patronage system: Australian and other “colonial” fellows of the Royal Society of London’, in International Science and National Scientific Identity, eds R. W. Home and S. G. Kohlstedt, Dordrecht, Boston, pp. 151–179.

Hunter, D., Bomford, R. B., and Russell, D. S. (1940) Poisoning by methyl mercury compounds, Quarterly Journal of Medicine, 9, 193–226.

Jensen, W. B. (2002) Mendeleev on the Periodic Law—Selected Readings 1869–1905, Cincinnati, Ohio.

Johnson, G. O., and Adkins, H. (1932) Certain factors influencing the yield of Grignard reagents and the ratio of R2Mg to RMgX, Journal of the American Chemical Society, 54, 1943–1947.
Certain factors influencing the yield of Grignard reagents and the ratio of R2Mg to RMgXCrossref | GoogleScholarGoogle Scholar |

Löhr, P. (1891) Ueber Alkylverbindungen des Cadmiums und des Magnesiums, Justus Liebig’s Annalen der Chemie, 261, 48–87.
Ueber Alkylverbindungen des Cadmiums und des MagnesiumsCrossref | GoogleScholarGoogle Scholar |

Macleod, R. (Ed.) (1988) The Commonwealth of Science: ANZAAS and the Scientific Enterprise in Australasia, 1888–1988, Melbourne.

Masson, O. (1891a) ‘The gaseous theory of solution’, in Report of the Third Meeting of the Australasian Association for the Advancement of Science, ed. J. Hector, Wellington, New Zealand, pp. 84–103.

Masson, O. (1891b) ‘On molecular volumes and boiling-points in relation to chemical character’, in Report of the Third Meeting of the Australasian Association for the Advancement of Science, ed. J. Hector, Wellington, New Zealand, pp. 103–106.

Masson, O. (1891c) ‘Does magnesium form alkyl compounds?’, in Report of the Third Meeting of the Australasian Association for the Advancement of Science, ed. J. Hector, Wellington, New Zealand, pp. 107–108.

Masson, O., and Wilsmore, N. T. M. (1891) Does magnesium form compounds with hydrocarbon radicles?, Proceedings of the Chemical Society, 7, 16–19.

Masters, A. F. (1990) A brief history of organometallic chemistry in Australia and New Zealand, Applied Organometallic Chemistry, 4, 389–418.
A brief history of organometallic chemistry in Australia and New ZealandCrossref | GoogleScholarGoogle Scholar |

Mendeleev, D. I. (2019) On the atomic volume of simple bodies, Bulletin for the History of Chemistry, 44, 109–115.

Mendelejeff, D. (1872) Die periodische Gesetzmässigkeit der chemischen Elemente, Annalen der Chemie und Pharmacie, VIII: Supplmentbanden, 2, 133–229.

Meyer, L. (1870) Die Natur der chemischen Elemente als function ihrer Atomgewichte, Annalen der Chemie und Pharmacie Supplementband, 7, 354–364.

Nye, M. J. (1986) Science in the Provinces, Berkeley, California.

Radford, J. (1978) The Chemistry Department of the University of Melbourne: Its Contribution to Australian Science 1854–1959, Melbourne.

Rae, I. D. (1988) ‘Chemists at ANZAAS: cabbages or kings?’, in The Commonwealth of Science: ANZAAS and the Scientific Enterprise in Australasia, 1888–1988, ed. R. MacLeod, Melbourne, pp. 166–195.

Rae, I. D. (2013) David Orme Masson, the periodic classification of the elements and his ‘Flap’ model of the periodic table, Historical Records of Australian Science, 24, 40–52.
David Orme Masson, the periodic classification of the elements and his ‘Flap’ model of the periodic tableCrossref | GoogleScholarGoogle Scholar |

Ramsay, W. (1881) Communications from the laboratory of the University College, Bristol, Journal of the Chemical Society, Transactions, 39, 49–53.

Rasmussen, S. C. (2021) Transmetalation: a fundamental organometallic reaction critical to synthesis and catalysis, ChemTexts, 7, 1.
Transmetalation: a fundamental organometallic reaction critical to synthesis and catalysisCrossref | GoogleScholarGoogle Scholar |

Rivett, A. C. D. (1939) Sir David Orme Masson, 1858–1937, Obituary Notices of Fellows of the Royal Society, 2, 454–464.

Rocke, A. J. (2019) Lothar Meyer’s pathway to periodicity, Ambix, 66, 265–302.
Lothar Meyer’s pathway to periodicityCrossref | GoogleScholarGoogle Scholar | 31645216PubMed |

Roscoe, H. E., and Schorlemmer, C. (1881) A Treatise on Chemistry, vol III, Organic Chemistry, Part I, the Chemistry of the Hydrocarbons and Their Derivates, London.

Russell, C. A. (1996) Edward Frankland: Chemistry, Controversy and Conspiracy in Victorian England, Cambridge, UK.

Selleck, R. J. W. (2013) Finding Home: the Masson Family, North Melbourne.

Seyferth, D. (2001a) Cadet’s Fuming Arsenical Liquid and the Cacodyl Compounds of Bunsen, Organometallics, 20, 1488–1498.
Cadet’s Fuming Arsenical Liquid and the Cacodyl Compounds of BunsenCrossref | GoogleScholarGoogle Scholar |

Seyferth, D. (2001b) Zinc Alkyls, Edward Frankland, and the beginnings of main-group organometallic chemistry, Organometallics, 20, 2940–2955.
Zinc Alkyls, Edward Frankland, and the beginnings of main-group organometallic chemistryCrossref | GoogleScholarGoogle Scholar |

Seyferth, D. (2009) The Grignard reagents, Organometallics, 28, 1598–1605.
The Grignard reagentsCrossref | GoogleScholarGoogle Scholar |

Strohmeier, W., and Seifert, F. (1961) Notiz zur Isolierung von Dialkylmagnesiumverbindungen aus Grignard-Lösungen, Chemische Berichte, 94, 2356–2357.
Notiz zur Isolierung von Dialkylmagnesiumverbindungen aus Grignard-LösungenCrossref | GoogleScholarGoogle Scholar |

Unidentified (H. E. R. and P. P. B.) (1890) Thomas Carnelley, Nature, 42, 522–523. 10.1038/042522b0

Wanklyn, J. A. (1861) XIV—On zinc-methyl, Quarterly Journal of the Chemical Society, 13, 124–129.
XIV—On zinc-methylCrossref | GoogleScholarGoogle Scholar |

Wanklyn, J. A. (1866) XII—On a new method of forming organo-metallic Bodies, Journal of the Chemical Society, 19, 128–130.
XII—On a new method of forming organo-metallic BodiesCrossref | GoogleScholarGoogle Scholar |

Wanklyn, J. A., and Chapman, E. T. (1866) XV.—On magnesium, Journal of the Chemical Society, 19, 141–144.
XV.—On magnesiumCrossref | GoogleScholarGoogle Scholar |

Weickhardt, L. (1989) Masson of Melbourne, Melbourne.

Wilsmore, N. T. M. (1891a) ‘Unsuccessful attempts to prepare magnesium ethyl’, in Report of the Third Meeting of the Australasian Association for the Advancement of Science, ed. J. Hector, Wellington, New Zealand, pp. 108–115.

Wilsmore, N. T. M. (1891b) ‘Note on magnesium iodide’, in Report of the Third Meeting of the Australasian Association for the Advancement of Science, ed. J. Hector, Wellington, New Zealand, p. 116.

Winkler, C. (1887) Mittheilungen über das germanium, Journal für praktische Chemie, 36, 177–209.
Mittheilungen über das germaniumCrossref | GoogleScholarGoogle Scholar |