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Christopher C. Cummins
Abstract: The chemistry of the element phosphorus offers a window into the diverse eld of inorganic
chemistry. Fundamental investigations into some simple molecules containing phosphorus reveal much
about the ramications of this elements position in the periodic table and that of its neighbors. Addition-
ally, there are many phosphorus compounds of commercial importance, and the industry surrounding
this element resides at a crucial nexus of natural resource stewardship, technology, and modern agriculture.
Questions about our sources of phosphorus and the applications for which we deploy it raise the provocative
issue of the human role in the ongoing depletion of phosphorus deposits, as well as the transfer of phos-
phorus from the land into the seas.
9
Phosphorus: Figure 1
From the Periodic Table with Nonmetals, Including Biogenic Elements, Above the Stair-Step Line
Stars to
Land & Sea
Biogenic elements are H, C, N, O, P, S in the nonmetals region of the periodic table, indicated by the heavy line.
Source: Adapted from a graphic found on http://www.openclipart.org.
lithium-ion batteries, which are used in phorus if chlorine is not even present in
consumer electronics (such as laptops) the products, such as lithium hexafluoro-
and automotive applications.4 So how is phosphate, that are the target of synthesis?
it made? The synthesis route begins with These industry standard processes suggest
the white form of elemental phosphorus, there is room for improvement: if manu-
a simple molecular form of the element facturers eliminated the use of chlorine
consisting of tetrahedral P4 molecules in the synthesis of important phosphorus
(Figure 2).5 White phosphorus is com- compounds in which chlorine is absent,
bined with elemental chlorine in order to both hazards and waste would be signi-
bring the phosphorus to the correct oxi- cantly reduced.
dation state (+5), and then, in a second Because our research has shown that it is
step, chloride is replaced by fluoride. indeed possible to derive organo-phospho-
This process is also frequently used to rus compounds directly from white phos-
synthesize many organo-phosphorus com- phorus, this is an opportunity for inor-
pounds that are important components of ganic chemistry to improve the safety and
catalysts used in the chemical industry.6 efciency of the manufacturing process.
In these applications, again, white phos- In one advance, we showed that phospho-
phorus is rst oxidized using chlorine, and rus-carbon bonds can be generated by
then the chloride provides the basis for the using white phosphorus together with a
formation of carbon-phosphorus bonds.7 source of organic radicals.9 Each of the six
But notably, elemental chlorine is hazard- phosphorus-phosphorus bonds present in
ous to use and ship, and environmental a molecule of white phosphorus absorbs
groups have called for an outright ban on two organic radicals in the process of being
it.8 So why use chlorine to oxidize phos- broken; each P4 tetrahedron is broken
Source: Generated by the author using the platon program. See A. L. Spek, Single-Crystal Structure Valida-
tion with the Program platon, Journal of Applied Crystallography 36 (2003): 713.
The box encloses one crystallographic unit cell. Source: Generated by the author using crystallographic coordi-
nates from M. Ruck et al., Fibrous Red Phosphorus, Angewandte Chemie International Edition 44 (2005), doi:10.1002/
anie.200503017.
bedded a diphosphorus moiety into the generation should not matter. Could there
stabilizing environment of a niobium be a way to access the P2 molecule by start-
complex (niobium is a transition metal; ing from a stable form of the element, rath-
it forms complexes by arranging sets of er than from an exotic niobium complex?
molecules or ionscalled ligandsaround We found the suggestion in a lightly cited
itself ), from which it could be released by 1937 paper that the photochemical conver-
a stimulus of mild heating.13 Carrying out sion of white phosphorus into the red form
the fragmentation reaction in the presence of the element may occur with P2 as the
of other molecules permitted the mapping key intermediary, which is initially gener-
of the reactivity patterns of diatomic phos- ated and subsequently polymerizes.14
phorus. One important result was the dis- We found by experiment (see Figure 5) that
covery that P2 easily undergoes addition to the addition of methyl isoprene to a solu-
unsaturated organic molecules, such as 1,3- tion of white phosphorus during irradia-
cyclohexadiene (see Figure 4). tion both inhibits the production of red
If diatomic molecular phosphorus is in- phosphorus and yields molecules in the
deed capable of direct combination with same class of organo-phosphorus com-
organic molecules, then the means of its pounds that we studied earlier in connec-
65 C
In the depicted sequence, transient P2 (not observed) combines with two molecules of 1,3-cyclohexadiene resulting
in four new P-C single bonds in the stable nal product (shown both as a line drawing and in a thermal ellipsoid
representation from a single-crystal X-ray diffraction analysis). Abbreviations: tBu is tert-butyl, Ar is aryl (spe-
cically 3,5-Me2C6H3), and Mes* is supermesityl. Source: Adapted from material published in N. A. Piro, J. S. Figueroa,
J. T. McKellar, and C. C. Cummins, Triple-Bond Reactivity of Diphosphorus Molecules, Science 313 (2006), doi:
10.1126/science.1129630.
tion with niobium-mediated access to di- phase As4 molecules, one heats grey arse-
phosphorus molecules.15 Hence, in effect nic (which has a layered sheet structure
and in principle, we have shown that in reminiscent of graphite or black phospho-
certain cases the hazardous and wasteful rus) to about 550 degrees C while flowing a
use of chlorine in the synthesis of organo- carrier gas over it. The As4 molecules, en-
phosphorus compounds can be replaced trained in the carrier gas, can be led into a
with a process relying on ultraviolet radia- solvent and used for reaction chemistry be-
tion. fore re-polymerization to grey arsenic can
take place. If condensed to a solid on a
A fter viewing the beautiful tetrahedral cold surface, the As4 condensate is yellow
arsenic, but it cannot be kept. Warming
molecular form of elemental phosphorus
in Figure 2, one might wonder whether this to room temperature or exposure to light
arrangement of phosphorus is unique to brings about a facile return to the grey
this particular element. Arsenic (As) lies form.16
just below phosphorus on the periodic ta- Phosphorus and arsenic lie on either side
ble, separated from it by the stair-step line of the divide (marked on Figure 1) separat-
dividing the metals from the nonmetals ing the metals from the non-metals. White
(see Figure 1). Once again, the periodicity phosphorus is stable enough that it can be
of chemical properties suggests that mol- stored as a pure liquid above its melting
ecular arsenic might adopt a similar tet- point of 44 degrees C and pumped into tank
rahedral structure to that of phosphorus. cars for shipping; while, conversely, sam-
Indeed, it does, but only in the gas phase ples of yellow arsenic are evanescent. We
where the molecules are well isolated from therefore wondered: would it be possible
one another, or in solution at low temper- to synthesize a stable substance whose tet-
ature and in the dark. To generate gas- rahedral molecules would be composed of
Methyl isoprene is the precursor to the original synthetic rubber. The reaction mechanism may involve P2 as a
reactive photo-generated intermediate.17 Source: Generated by the author using data from Daniel Tofan and Chris-
topher C. Cummins, Photochemical Incorporation of Diphosphorus Units into Organic Molecules, Angewandte
Chemie International Edition 49 (2010), doi:10.1002/anie.201004385.
Figure 6
From the Commodity-Chemical P4 Molecule to the Unstable As4 Molecule
What are the properties of substances composed of tetrahedral molecules of mixed composition? Source: Adapted
from Brandi M. Cossairt and Christopher Cummins, Properties and Reactivity Patterns of AsP3: An Experimental
and Computational Study of Group 15 Elemental Molecules, Journal of the American Chemical Society 131 (42) (2009),
doi:10.1021/ja906294m.
a mixture of phosphorus and arsenic (see provides a benchmark for theorists work-
Figure 6)? To test this idea, we made a ni- ing on the a priori prediction of properties;
obium complex carrying a P33 unit, and heavy elements pose the greatest challenge
combined this with a source of arsenic in this regard. The elements in the AsP3
(3+), effectively knitting together the neu- molecule are packaged together in a 1:3
tral AsP3 molecule in a selective fashion.18 ratio at the molecular level; and now this
The new substance turned out to have a substance is readily available as a starting
waxy appearance much like that of white material. Substitution of a single nitrogen
phosphorus, and it could be puried by atom into the P4 tetrahedron has scarcely
sublimation, wherein the pure material is been considered; one possibility involves
condensed onto a cold probe. Because of stabilization inside a recently discovered
the volatile nature of AsP3, we and our col- spherical B80 molecule that is analogous to
laborators determined its properties by a Buckminsterfullerene (C60).20
variety of techniques, including electron
diffraction, microwave spectroscopy, and
photoelectron spectroscopy.19 Obtaining
To ask why diatomic phosphorus is nei-
ther stable nor prevalent is really to ask a
gas-phase property data on a simple mol- larger question: why is elemental phospho-
ecule containing a heavy element (arsenic) rus not found on Earth as a pure substance,
Source: Generated by the author using the program MarvinSketch. Marvin is used for drawing,
displaying, and characterizing chemical structures, substructures, and reactions. See ChemAxon,
Marvin 6.1.3 (2014), http://www.chemaxon.com.
an unmodied pig, concerns about this identify ways of using this limited resource
creative kind of genetic engineering have that minimize waste, but we acknowledge
effectively blocked its adoption thus far. our limited ability to grapple with the con-
The chemistry of an element is a fasci- sequences of enormous demand for phos-
nating thing, and we have explored several phorusa markedly limited resource
of the issues that flow naturally from ask- stemming from a rapidly rising human
ing questions about where an element population. Phosphorus, therefore, is in-
comes from, what we use it for, and how teresting not only for its chemistry but
we might gain an improved understanding also in light of the rich texture of its larg-
of it. Motivated to study phosphorus by cu- er story, only one of the many stories that
riosity and a desire to expand on funda- emerge when we view inorganic chem-
mental science, we have come to appreci- istry from the perspective of a single ele-
ate the vital role played by this relatively ment.
precious element that forms the inorganic
backbone of dna, the energy currency of
atp, and the main component of bones and
teeth. We have demonstrated the ability to