title: Rapid Synthesis of Redox-Active Dodecaborane B12(OR)12Clusters Under Ambient Conditions.
abstract: We have developed a fast and efficient route to obtain perfunctionalized ether-linked alkyl and benzyl derivatives of thecloso-[B12(OH)12]2-icosahedral dodecaborate cluster via microwave-assisted synthesis. These icosahedral boron clusters exhibit three-dimensional delocalization of the cage-bonding electrons, tunable photophysical properties, and a high degree of stability in air in both solid and solution states. A series ofcloso-[B12(OR)12]2-,hypocloso-[B12(OR)12]1-andhypercloso-[B12(OR)12]0clusters have been prepared with reaction times ranging from hours to several minutes. This method is superior to previously reported protocols since it dramatically decreases the reaction times required and eliminates the need for inert atmosphere conditions. The generality of the new microwave-based method has been further demonstrated through the synthesis of several new derivatives, which feature redox potentials up to 0.6 V more positive than previously known B12(OR)12cluster compounds. We further show how this method can be applied to a one-pot synthesis of hybrid, vertex-differentiated species B12(OR)11(OR) that was formerly accessible only via multi-step reaction sequence.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles 607 Charles E. Young Drive East, Los Angeles, California 90095-1569.
authors.forename: Alex I
authors.initials: AI
authors.lastname: Wixtrom
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles 607 Charles E. Young Drive East, Los Angeles, California 90095-1569.
authors.forename: Yanwu
authors.initials: Y
authors.lastname: Shao
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles 607 Charles E. Young Drive East, Los Angeles, California 90095-1569.
authors.forename: Dahee
authors.initials: D
authors.lastname: Jung
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093-0358.
authors.forename: Charles W
authors.initials: CW
authors.lastname: Machan
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles 607 Charles E. Young Drive East, Los Angeles, California 90095-1569.
authors.forename: Shaunt N
authors.initials: SN
authors.lastname: Kevork
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles 607 Charles E. Young Drive East, Los Angeles, California 90095-1569.
authors.forename: Elaine A
authors.initials: EA
authors.lastname: Qian
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles 607 Charles E. Young Drive East, Los Angeles, California 90095-1569.
authors.forename: Jonathan C
authors.initials: JC
authors.lastname: Axtell
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles 607 Charles E. Young Drive East, Los Angeles, California 90095-1569.
authors.forename: Saeed I
authors.initials: SI
authors.lastname: Khan
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093-0358.
authors.forename: Clifford P
authors.initials: CP
authors.lastname: Kubiak
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles 607 Charles E. Young Drive East, Los Angeles, California 90095-1569.
authors.forename: Alexander M
authors.initials: AM
authors.lastname: Spokoyny