ill

IT'S ELEMENTAL!

that have sections on the photochemistry

CHROMIUM of metal complexes.

The chromous ion is very special to me,
as it launched my work on electron tun-
HARRY B. GRAY, CALIFORNIA INSTITUTE OF TECHNOLOGY neling through proteins. In the early 70s,
colleagues and I used aqueous Cr(II) to
the triply bonded oxoclirornium(V) unit, and transfer electrons to the blue copper cen-

I
WAS D E S T I N E D TO WORK ON C H R O -
mium: My mother's name was Ruby Curtis R. Hare and I interpreted its d-d spec- ters in spinach plastocyanin, bean plas-
Mom loved the stunning red gem- trum [Inorg. Chem., 1,363 (1962)]. (Later, with tocyanin, Rhus vernicifera laccase, and stel-
stone, b u t she didn't know there Carl J. Ballhausen and V M. Miskowski, I lacyanin [Proc. Natl. Acad. Sci. USA, 6 9 ,
would be a ruby laser, and neither did worked on the spectra of chro- 30 (1972)}. Our experiments
I, during the late 1940s and early '50s mate and halochromates, which, showed that electron transfers
when I was experimenting with chromi- like dichromate, are all in the VI to some copper centers were
um compounds in the basement of our oxidation state made famous by much slower than others, and we
house. I had quite a nice lab, and I re- Julia Roberts in the movie "Erin now know that in most bio-
member that Mom was worried that I Brockovich.") logical reactions electrons must
would blow myself up, especially when I During the next year at Co- tunnel through many bonds to
used dichromate as an oxidant in spec- lumbia University Nancy Beach reach their destinations. Much
tacularly exothermic redox reactions. and I worked on zerovalent CELEBRATING later, in work reminiscent of
chromium: "We reported that the C&EN'S Taube's, Israel Pecht and Ole
UV spectrum of its carbon mon- 80TH Farver identified one of t h e
oxide complex, chromium hexa- ANNIVERSARY Cr(III)-protein binding sites af-
carbonyl, exhibits two very in- ter Cr(II) reduction. In so doing,
tense absorptions that are attributable to they estimated how far an electron had to
metal-to-ligand charge-transfer (MLCT) travel in its journey to a copper active site.
transitions. Amazingly our interpretation of Many investigators have explored the
the hexacarbonylMLCTspectrum has with- spectroscopy and chemistry of the d-d ex-
stood 40 years of theoretical scrutiny al- cited states of octahedral Cr(III), and the
though the positions ofthe lowest d-d excita- excited doublet, in particular, has had a
S E E I N G R E D Chromium impurities tions have beenrevisedby density functional long and glorious (some say checkered) his-
in corundum give rubies their theorists. The excited-state dynamics of the tory Whether the doublet undergoes as-
distinctive red color. molecule are nowunderstood in great detail, sociative substitution is still debated when
and for that reason, zerovalent chromium "inorganikers" gather for discussions of
In college, I worked on the analytical usually makes an appearance in textbooks mechanisms. In 1985, with Bruce S. Brun-
chemistry of chromium and three of its schwig and other colleagues, we examined
neighbors: vanadium, niobium, and mo- the rates of oxidation of reduced blue-cop-
CHROMIUM AT A GLANCE
lybdenum. Although I loved the chal- per proteins by this relatively long-lived
lenge of analyses, the inorganic Name: From the Greek chroma, color. and powerfully oxidizing Cr(III) reagent,
research that Fred Basolo and Atomic mass: 52.00. in one of the early demonstrations of elec-
Ralph Pearson were doing at History: Discovered in 1780 by tron tunneling through folded polypep-
Northwestern University ex- Nicholas Louis Vauquelin. tides {Inorg. Chem., 24,3743 (1985)}.
cited me even more, and I Occurrence: Isolated mostly from All in all, I have worked on six oxida-
joined their group in 1958. The chromite ore. tion states of chromium. In recent times,
late '50s were the glory days of in- Appearance: Blue white, hard and brit- and in collaboration with Zeev Gross of
organic mechanisms, and chromium was tle metal. Technion-Israel Institute of Technology,
one of the big stars. The chromous ion, Behavior: Resists oxidation in air. Many our group has managed to prepare
which is a powerful reductant and can at- chromium compounds are toxic. Chro- chromium corroles in four oxida-
tack oxidants at close range, is substitution mates are corrosive to skin and tis- tion states, I I I through VI, al-
labile; and, as all inorganic chemists know, sue. Chromium itself is a human poi- though "VI" turned out to be V
the chromium product of the reaction, son if ingested and is suspected of complexed to an oxidized corrole.
Cr(III), is substitution inert. H e n r y being a carcinogen. The presence of The joint lechnion-California In-
Taube's famous experiment demonstrat- chromium impurities in gems is often re- stitute of Technology research on aer-
ing atom transfer from chloropentaam- sponsible for their brilliant colors. obic oxidations catalyzed by chromium
minecobalt(III) to chromous ion relied Uses: Essential trace element in hu- corroles is the latest chapter in my affair
on these properties of two of the more mans that plays a role in glucose me- with element 24.
common oxidation states of the element. tabolism. In alloys, chromium can serve
In my work in Copenhagen in t h e as a protective coating from oxidation Harry B. Gray is the Arnold O. Beckman Pro-
spring of 1961,1 became fascinat- and comprises up to 18% of stainless fessor of Chemistry at Caltech. He received the
ed with oxo complexes, especially steel. Its oxides are often used as pig- NationalMedal of Science in 1986 andthe Priest-
the vanadyl and chromyl ions. The ments, for tanning leather, and in high- ley Medalin 1991; in 2003, he receivedthe Nichols
garnet-red ammonium penta- quality recording tapes. and WhelandMedals as wellas the NationalAcad-
chlorooxochromate(V) contains emy ofSciencesAward in Chemical Sciences.

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