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AVAILABLE
TECHNOLOGIES |
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Novel
Catalyst Exchanges Deuterium or Tritium into Organic and Organometallic
Compounds
IB-1698
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APPLICATION
OF TECHNOLOGY:
Preparing
deuterium- or tritium-labeled organic and organometallic compounds
for:
- Manufacturing
pharmaceuticals, chemicals, and agricultural products
- Spectroscopic
experiments
- Research
on chemical structure and reaction mechanisms
- Analytical
tracers
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ADVANTAGES:
- Catalyzes
hydrogen/deuterium (H/D) exchange from the least expensive
deuterium and tritium source, heavy water, into organic
and organometallic compounds with activated or unactivated
protons
- Enables
the profitable production of new commercial deuterium- and
tritium-labeled compounds and will make others less expensive
to prepare
- Employs
a catalyst that is easy to remove from products, is stable
in air, and is moderately stable in water
- Unlike
processes using platinum-based catalysts, strongly acidic
conditions are not necessary, allowing exchange into organic
compounds that would destabilize in the presence of an acid
- Catalytic
activity is higher than that of previously reported rhodium
and iridium complexes
- The
H/D exchange occurs under conditions that are inexpensive
and easy to achieve: heating temperatures of between 70
and 150 degrees C and atmospheric pressure
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ABSTRACT:
Robert Bergman and Steven Klei have discovered a class of
transition metal compounds that catalyze the exchange of deuterium
from heavy water (D2O) into a wide range of organic and organometallic
compounds that are otherwise difficult to deuterate. The process
is ideal for commercialization for several reasons. It uses
the least expensive source of deuterium, heavy water, for
the exchange, overcoming the fact that water is normally non-reactive
with organic compounds, and when it is reactive, it typically
participates in H/D exchange only with activated protons.
The Berkeley Lab catalyst causes heavy water to exchange with
both activated and unactivated protons. In addition, while
some other isotope labeling processes require very high temperatures
and pressures, this exchange occurs under moderate temperatures
and atmospheric pressure, minimizing processing costs. Furthermore,
the most active catalyst discovered by Bergman and Klei is
air stable and can be prepared in two high-yielding steps
from commercially available compounds. This breakthrough promises
to make deuterium- and tritium-labeled organic and organometallic
materials less costly and more readily available.
The general structure of the two types of transition metal
complexes serving as catalysts in this process are delineated
in the figure above where, in the ionic model, A1 and A2 represent
any ligand that can donate six electrons, L1 and L2 represent
charge neutral two-electron donors, X1 , X2 , X3 , X4 , and
X5 stand for two-electron donors, M is a group VIII metal,
and Y is a negatively charged anion capable of creating a
charge-neutral complex. The starting materials then, are 18
electron species that are assumed to form a 16 electron catalytically
active species, by either dissociating a ligand (X1 or X2),
i.e. ionizing, in the case of type I, or reductively eliminating
a small molecule (X3, X4 or X5) in the case of type II.
Catalysts of the types described above can be prepared by
known methods. When the compound is contacted with a source
of deuterium and a substrate molecule, and the combination
is heated at a temperature between 75 and 150 degrees Celsius,
one or more deuterium and/or tritium atoms exchanges with
one or more protons of the organic substrate molecule. The
now deuterium-tagged organic molecule can be separated or
isolated by readily available techniques.
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STATUS:
- U.S. Patent
#6,794,522
- Available for Licensing
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FOR
MORE INFORMATION PLEASE SEE:
- Golden,
J. T.; Andersen, R. A.; Bergman, R. G. "Exceptionally Low-Temperature
Carbon-Hydrogen/Carbon-Deuterium Exchange Reactions of Organic
and Organometallic Compounds, Including Aliphatic and Aromatic
Hydrocarbons, Catalyzed by the Cp*(PMe3)IrH(L)+ Cation"
J. Am. Chem. Soc., 2001, 123, 5837-5838.
- Klei,
S. R.; Tilley, D. T.; Bergman, R. G. "An Observable Silene/Silylene
Rearrangement in a Cationic Iridium Complex" Organometallics,
2001, 20, 3220-3222.
- Klei, S.R.; Golden, J.T.; Burger, P.; and Bergman, R.G. "Cationic Ir(III) Alkyl and Hydride Complexes: Stoichiometric
and Catalytic C-H Activation by Cp*(PMe3)Ir(R)(X) in Homogeneous
Solution" J. of Molecular Catalysis A: Chemical, Vol. 189, Issue 1, Oct. 1002, 79-94.
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REFERENCE
NUMBER: IB-1698
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CONTACT:
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Technology
Transfer Department
E.O. Lawrence Berkeley National Laboratory
MS 90-1070
Berkeley, CA 94720
(510) 486-6467 FAX: (510) 486-6457
TTD@lbl.gov |
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