Рутений Made It Possible

Ruthenium, or Рутений in Russian, was named for Russia. We should call the element russium--that would at least be more historically descriptive--but ruthenium it is.* The first detectable amounts came from platinum ores in the Ural mountains--first discovered in the 1820's. The element is exceedingly rare--and thus expensive--and yet it too has its unique chemical niche. 

Ruthenium is the first element in the series 1 to 44 which can be fully stripped of 8 electrons to give a stable oxidation state of VIII.** Step just one atomic number backwards, to technetium, and there aren't 8 valence electrons to lose--only 7; step one element to the right, to rhodium, and the nucleus is already too electronegative to give up more than 6 electrons.  This makes ruthenium special--its willingness to fully yield to rapacious oxygen.

Ruthenium isn't really famous for much. It enjoyed brief fame in 1952 when ruthenocene was prepared by analogy to ferrocene, but it always seemed a little under-represented in catalysis until a chemist named Robert Grubbs (originally from Possum Trot holler in Kentucky), put ruthenium on the map with his Nobel-prize winning work centered around olefin metathesis.

"Olefin metathesis" has interesting history as a term--taken apart, "olefin" comes from oléfiant which means oil-forming and which ultimately comes from the roots oleum + facere. Olefin is an old word as chemistry words go--not so old to be practically archaic like oleum or vitriol, but still old. The modern term for olefin is alkene--organic hydrocarbons having one or more unsaturated double bond. The terms "polyunsaturated fat" and "trans fat" refer to olefins, FWIW.

Metathesis is a special word meaning rearrangement. There's a grammatical sense of the word which means transposition, and the chemical sense is just a metaphor. If we let the equal sign be a double bond, olefin metathesis refers to

a=b + c=d --> a=c + b=d.

See what happened there? Transposition.
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*Ruthenia corresponded to a much smaller region of what is now in the Ukraine. The Ural region was unknown to the Romans.
**Wikipedia notes claims to the existence of Fe(VIII) as in FeO₄ but the claim is tentative.

"Rutherford was an artist. All his experiments had style."

Ernest Rutherford (1871-1937)

Ernest Rutherford reminds me of Michael Faraday. Born in humble circumstances in faraway New Zealand, he travelled to the mother country to study physics. Like Faraday, equal opportunity earned him a place with the best of his day and this meant the Cavendish Laboratory at the University of Cambridge. Rutherford must have witnessed J.J. Thomson's discovery of the electron there in 1897 but there's no record of him taking part in that work. It didn't matter--he had enough in him for two careers in science and a Nobel Prize of his own. And one of Rutherford's great achievements was the accidental undoing of his mentor's plum-pudding model of the atom.

Rutherford's first independent work was the unravelling of radioactivity along with Fredrick Soddy.  More on this later. But first, I want to close a loop I opened a few posts ago by hinting that I had found an inconsistency. I was referring to Richard Rhodes' account of Rutherford receiving the 1908 Nobel Prize in Chemistry:

An eyewitness to the ceremonies said Rutherford looked ridiculously young--he was thirty-seven--and made the speech of the evening. He announced his recent confirmation, only briefly reported the month before, that the alpha particle was in fact helium. The confirming experiment was typically elegant. Rutherford had a glassblower make him a tube with extremely thin walls. He evacuated the glass tube and filled it with radon gas, a fertile source  of alpha particles. The tube was gas tight, but its thin walls allowed alpha particles to escape. Rutherford surrounded the radon tube with another gas tube, pumped out the air between the two tubes and sealed off the space. 'After some days,' he told his Stockholm audience triumphantly, 'a bright spectrum of helium was observed in the outer vessel.' Rutherford's experiments still stun with their simplicity. 'In this Rutherford was an artist,' says a former student. 'All his experiments had style.' 

~Richard Rhodes in "The Making Of The Atomic Bomb"

Rhodes' book is a favorite of mine and I've read it a couple times. But Rhodes makes no mention of Soddy and Ramsey's proof five years earlier that the alpha particle was helium. According to Wikipedia:

In 1903, with Sir William Ramsay at University College London, Soddy verified that the decay of radium produced alpha particles composed of positively charged nuclei of helium. In the experiment a sample of radium was enclosed in a thin walled glass envelope sited within an evacuated glass bulb. Alpha particles could pass through the thin glass wall but were contained within the surrounding glass envelope. After leaving the experiment running for a long period of time a spectral analysis of the contents of the former evacuated space revealed the presence of helium. This element had recently been discovered in the solar spectrum by Bunsen and Kirchoff.* link

This account essentially parallels the elegant (but later) experiment announced in 1908 by Rutherford and described by Rhodes with the exception of radium instead of radon as the source of alpha particles. However, my review of the 1903 Ramsey & Soddy paper cited by the Wiki actually describes a much different and less elegant experiment. link
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*Also, Bunsen and Kirchoff didn't find helium in the solar spectrum--Lockyer did: link