Near-IR absorbing nickel(II) porphyrinoids prepared by regioselective insertion of silylenes into antiaromatic nickel(II) norcorrole.
The treatment of an antiaromatic norcorrole Ni(II) complex with a kinetically stabilized silylene provided ring-expansion products in excellent yields through the highly regio- and stereoselective insertion into the β-β pyrrolic CC bonds. The resultant Ni(II) porphyrinoid monoinsertion product exhibited relatively strong near-IR absorption bands due to the small HOMO-LUMO gap in spite of the disrupted cyclic π-conjugation by the silicon atom.
Department of Applied Chemistry, Graduate School of Engineering Nagoya University, Nagoya, 464-8603 (Japan).
Takaki
T
Fukuoka
Kenya
K
Uchida
Young Mo
YM
Sung
Ji-Young
JY
Shin
Shintaro
S
Ishida
Jong Min
JM
Lim
Satoru
S
Hiroto
Ko
K
Furukawa
Dongho
D
Kim
Takeaki
T
Iwamoto
Hiroshi
H
Shinokubo
NIR absorption; antiaromaticity; insertion; porphyrinoids; silylenes