BROWSE

Related Scientist

Researcher

박세훈
분자활성 촉매반응 연구단
more info

Comparative Investigations of Cp*-Based Group 9 Metal-Catalyzed Direct C-H Amination of Benzamides

Cited 67 time in webofscience Cited 0 time in scopus
516 Viewed 39 Downloaded
Title
Comparative Investigations of Cp*-Based Group 9 Metal-Catalyzed Direct C-H Amination of Benzamides
Author(s)
Figg, TM; Sehoon Park; Juhyeon Park; Sukbok Chang; Djamaladdin G. Musaev
Publication Date
2014-08
Journal
ORGANOMETALLICS, v.33, no.15, pp.4076 - 4085
Publisher
AMER CHEMICAL SOC
Abstract
Key mechanistic features of the [Cp*MCl2]2(M = Ir, Rh, Co; all are in group 9) catalyzed C−H amination of benzamides with organic azides were investigated with a strong emphasis on the metal ef fects on the reaction mechanism, revealing that the Rh- and Ir-catalyzed reactions follow a similar reaction profile, albeit with different individual kinetic and thermodynamic parameters. The observation that the Irbased system was much superior in terms of the rates and efficiency in comparison to Rh was attributed to the intrinsically strong relativistic ef fects in iridium. While a cobalt system [Cp*CoIII] showed little catalytic activity for most azides examined, plausible [(BA)(Cp*)CoNR]+ intermediates of these reactions were characterized as a “Co(III)-nitrenoid radical” species with a weak (“one electron−two center type”) Co−NPh bond. Its Rh and Ir analogues are characterized as diamagnetic metal nitrenoids with a strong MNR double bond. The provided experimental and computational investigations indicate that the rate-limiting step of the reaction resides in the final stage (protodemetalation) that takes place via a concerted metalation−deprotonation (CMD) mechanism. While experimental measurements of thermodynamic parameters were in good agreement with DFT calculations, theoretical predictions on the electronic nature of key intermediates and energy barriers were successfully used to rationalize the experimentally observed reactivity pattern.
URI
https://pr.ibs.re.kr/handle/8788114/1478
ISSN
0276-7333
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
Files in This Item:
30.pdfDownload

qrcode

  • facebook

    twitter

  • Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.
해당 아이템을 이메일로 공유하기 원하시면 인증을 거치시기 바랍니다.

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

Browse