title: Reactivity of [1(2,3)4]pentamantane (Td-pentamantane): a nanoscale model of diamond.
abstract: To model the chemical properties of the hydrogen-terminated nanodiamond {111} and {110} surfaces, the functionalizations of the higher diamondoid [1(2,3)4]pentamantane were studied. [1(2,3)4]Pentamantane reacts selectively with neat bromine to give the medial 2-mono- and 2,4-disubstitution products. In contrast, oxidation with nitric acid as well as single-electron-transfer oxidation involving the [1(2,3)4]pentamantane radical cation results in apical C7-substitutions. This substitution pattern dominates in the free-radical bromination under phase-transfer catalytic conditions that gives a mixture of 7- and 2-bromo[1(2,3)4]pentamantane in a 95:5 ratio. Replacement of the functional groups in [1(2,3)4]pentamantane occurs without isomerization. This was demonstrated for the interconversions of the bromo and hydroxy derivatives as well as for the preparation of [1(2,3)4]pentamantyl-7-thiol from 7-hydroxy[1(2,3)4]pentamantane. Thus, the selective functionalization of hydrogen-terminated nanodiamonds is possible by means of reactions with common electrophiles-oxidizers.
authors.affiliation: Institut für Organische Chemie and Institut für Anorganische und Analytische Chemie, Justus-Liebig University, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany.
authors.forename: Andrey A
authors.initials: AA
authors.lastname: Fokin
authors.forename: Peter R
authors.initials: PR
authors.lastname: Schreiner
authors.forename: Natalie A
authors.initials: NA
authors.lastname: Fokina
authors.forename: Boryslav A
authors.initials: BA
authors.lastname: Tkachenko
authors.forename: Heike
authors.initials: H
authors.lastname: Hausmann
authors.forename: Michael
authors.initials: M
authors.lastname: Serafin
authors.forename: Jeremy E P
authors.initials: JE
authors.lastname: Dahl
authors.forename: Shenggao
authors.initials: S
authors.lastname: Liu
authors.forename: Robert M K
authors.initials: RM
authors.lastname: Carlson