TY - JOUR
T1 - Why do the [PhSiO1.5]8,10,12 cages self-brominate primarily in the ortho position? Modeling reveals a strong cage influence on the mechanism
AU - Hashemi, Daniel
N1 - (PhSiO1.5)8,10,12 cages are bulky, electron withdrawing like CF3; yet self-brominate (60 °C), favoring ortho substitution: PhT8 (≈85%), PhT10 (≈75%) and PhT12 (60%). First-principles calculations suggest bromination initiates when Br2 is "trapped" via H-bonding to ortho-H's, followed by polarization via stro
PY - 2014/10/20
Y1 - 2014/10/20
N2 - (PhSiO 1.5 ) 8,10,12 cages are bulky, electron withdrawing like CF 3 ; yet self-brominate (60 °C), favoring ortho substitution: PhT 8 (≈85%), PhT 10 (≈75%) and PhT 12 (60%). First-principles calculations suggest bromination initiates when Br 2 is “trapped” via H-bonding to ortho -H's, followed by polarization via strong interactions with cage faces , possibly cage LUMOs.
AB - (PhSiO 1.5 ) 8,10,12 cages are bulky, electron withdrawing like CF 3 ; yet self-brominate (60 °C), favoring ortho substitution: PhT 8 (≈85%), PhT 10 (≈75%) and PhT 12 (60%). First-principles calculations suggest bromination initiates when Br 2 is “trapped” via H-bonding to ortho -H's, followed by polarization via strong interactions with cage faces , possibly cage LUMOs.
UR - https://pubs.rsc.org/en/content/articlelanding/2014/cp/c4cp03997a/unauth
M3 - Article
JO - Phys. Chem. Chem. Phys.
JF - Phys. Chem. Chem. Phys.
ER -