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Reactivities of the Prism‐Shaped Diamondoids [1(2)3]Tetramantane and [12312]Hexamantane (Cyclohexamantane)
Author(s) -
Fokin Andrey A.,
Tkachenko Boryslav A.,
Fokitalie A.,
Hausmann Heike,
Serafin Michael,
Dahl Jeremy E. P.,
Carlson Robert M. K.,
Schreiner Peter R.
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200801867
Subject(s) - diamondoid , halogenation , isomerization , electrophile , tripod (photography) , chemistry , diamond , density functional theory , reagent , nanodiamond , derivative (finance) , computational chemistry , photochemistry , stereochemistry , combinatorial chemistry , organic chemistry , molecule , physics , optics , economics , financial economics , catalysis
Functionalized nanodiamonds : 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 (see picture). The attachment points define the use of these diamond‐like molecules as geometric building blocks for a variety of applications.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 CH 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 CH 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.