Noble reactions for the actinides: safe gold-based access to organouranium and azide complexes

Journal Article · Tue Jan 01 04:00:00 EST 2008 · Angewandte Chemie. International Edition in English

OSTI ID:956621

Thomson, Robert K ^[1]; Graves, Christopher R ^[1]; Scott, Brian L ^[1]; Kiplinger, Jaqueline L ^[1]

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1. Los Alamos National Laboratory

Gold has had a profound impact on organic chemistry; its compounds are spectacular catalysts for many organic transformations involving the formation of C-C, C-O, C-N and CoS bonds, and have enabled unprecedented pathways for the functionalization of C-H and C-C bonds. In general, gold complexes have not been exploited as reagents in organometallic or inorganic chemistry, although a few gold(l) aryl and alkynyl compounds have been reported to undergo transmetalation with transition metal complexes. We have been developing methods for functionalizing uranium complexes and have shown that Cu(l)-X reagents effect the oxidation of uranium with formation of U-X bonds, providing easy chemical control over uranium in oxidation states ranging from U{sup III}{yields}U{sup VI}. Although a logical approach for the direct generation of U-carbon and U-azide bonds, this Cu-based platform is limited in scope as it only works for pure and isolable copper compounds. This is problematic given the instability of organocuprates and copper azides, which can detonate violently as isolated solids. As such, this route has been confined to the synthesis of select uranium phenylacetylide complexes. Over the past few years, a variety of stable gold(l) alkyl, alkenyl, aryl, alkynyl, and azide complexes have been reported, propelling us to investigate their potential as reagents within the oxidative functionalization platform. Unlike the related CU{sup I} systems, Au{sup I} reagents are easily derivatized, and are safe to handle and isolate. Herein, we report that gold(l)-phosphine compounds can undergo a new class of reaction, and are excellent reagents for the oxidative functionalization of uranium with azide and carbon anions.

• Research Organization: Los Alamos National Laboratory (LANL)
• Sponsoring Organization: DOE
• DOE Contract Number: AC52-06NA25396
• OSTI ID: 956621
• Report Number(s): LA-UR-08-07806; LA-UR-08-7806
• Journal Information: Angewandte Chemie. International Edition in English, Journal Name: Angewandte Chemie. International Edition in English; ISSN 0570-0833; ISSN ACIEAY
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
ACTINIDES
ANIONS
AZIDES
CARBON
CATALYSTS
CHEMISTRY
COMPLEXES
CONTROL
COPPER
COPPER COMPOUNDS
GOLD
GOLD COMPLEXES
INSTABILITY
OXIDATION
POTENTIALS
REAGENTS
SOLIDS
SYNTHESIS
TRANSFORMATIONS
TRANSITION ELEMENTS
URANIUM
URANIUM COMPLEXES
VALENCE