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Controlling the Regioselectivity of the Hydrosilylation Reaction in Carbon Nanoreactors
Author(s) -
Solomonsz William A.,
Rance Graham A.,
Suyetin Mikhail,
La Torre Alessandro,
Bichoutskaia Elena,
Khlobystov Andrei N.
Publication year - 2012
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.201201542
Subject(s) - nanoreactor , regioselectivity , hydrosilylation , catalysis , carbon fibers , chemistry , nanoparticle , alkyne , covalent bond , carbon nanotube , molecule , adsorption , chemical engineering , photochemistry , materials science , organic chemistry , nanotechnology , composite number , engineering , composite material
Hollow graphitized carbon nanofibres (GNF) are employed as nanoscale reaction vessels for the hydrosilylation of alkynes. The effects of confinement in GNF on the regioselectivity of addition to triple carbon–carbon bonds are explored. A systematic comparison of the catalytic activities of Rh and RhPt nanoparticles embedded in a nanoreactor with free‐standing and surface‐adsorbed nanoparticles reveals key mechanisms governing the regioselectivity. Directions of reactions inside GNF are largely controlled by the non‐covalent interactions between reactant molecules and the nanofibre channel. The specific π–π interactions increase the local concentration of the aromatic reactant and thus promote the formation of the E isomer of the β‐addition product. In contrast, the presence of aromatic groups on both reactants (silane and alkyne) reverses the effect of confinement and favours the formation of the Z isomer due to enhanced interactions between aromatic groups in the cis ‐orientation with the internal graphitic step‐edges of GNF. The importance of π–π interactions is confirmed by studying transformations of aliphatic reactants that show no measurable changes in regioselectivity upon confinement in carbon nanoreactors.