Reactivities of the prism-shaped diamondoids [1(2)3]tetramantane and [12312]hexamantane (cyclohexamantane).
Various functional groups have been incorporated into the structures of the naturally occurring diamondoids [1(2)3]tetramantane and [12312]hexamantane (cyclohexamantane), which represent hydrogen-terminated prism-shaped nanodiamonds. The selectivities of the C-H substitutions in [1(2)3]tetramantane depend on the reagent employed and give products substituted at either central (through bromination) or peripheral (through nitroxylation and photo-oxidation) positions. The hydrogen-coupled electron-transfer mechanism of C-H nitroxylation with the model electrophile NO(2)(+)...HNO(3) was verified computationally at the B3PW91 and MP2 levels of theory by utilizing the 6-31G(d) and cc-pVDZ basis sets. The thermodynamically controlled nitroxylation/isomerization of [1(2)3]tetramantane allows the preparation of peripherally trisubstituted derivatives, which were transformed into tripod-like nanodiamond building blocks. The bromination of cyclohexamantane selectively gives the 2-bromo derivative, reproducing the chemical behavior of the {111} surface of the hydrogen-terminated diamond.
Fokin
Andrey A
AA
Department of Organic Chemistry, Kiev Polytechnic Institute pr. Pobedy 37, 03056 Kiev, Ukraine. aaf@xtf.ntu-kpi.kiev.ua
Tkachenko
Boryslav A
BA
Fokina
Natalie A
NA
Hausmann
Heike
H
Serafin
Michael
M
Dahl
Jeremy E P
JE
Carlson
Robert M K
RM
Schreiner
Peter R
PR