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Literature DB >> 28922498

C(sp³ )-H Bond Activation by Vinylidene Gold(I) Complexes: A Concerted Asynchronous or Stepwise Process?

Johannes E M N Klein^1,2, Gerald Knizia³, Laura Nunes Dos Santos Comprido⁴, Johannes Kästner⁵, A Stephen K Hashmi^4,6.

Abstract

A detailed analysis of the C(sp3 )-H activation process by vinylidene AuI complexes is described based on an intrinsic bond orbital analysis. Based on our analysis this event can be divided into three phases: (i) hydride transfer, (ii) C-C bond formation, and (iii) σ to π rearrangement of the lone pair coordinated to Au. Small perturbations of the system lead to either a concerted asynchronous reaction, or a stepwise reaction featuring an intermediate with a C-H-C three-centre two-electron (3c-2e) bond. The role of π-donating substituents is highlighted and provides a way of controlling reactions of this type in future experimental studies.

Entities: Chemical Species

Keywords: C−H activation; bond orbital analysis; computational chemistry; gold(I); reaction mechanisms

Year: 2017 PMID： 28922498 DOI： 10.1002/chem.201703815

Source DB: PubMed Journal: Chemistry ISSN： 0947-6539 Impact factor: 5.236

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Cited

8 in total

1. Monoaurated vs. diaurated intermediates: causality or independence?

Authors: Mariarosa Anania; Lucie Jašíková; Jan Zelenka; Elena Shcherbachenko; Juraj Jašík; Jana Roithová
Journal: Chem Sci Date: 2019-12-13 Impact factor: 9.825

2. Efficient Computation of Geometries for Gold Complexes.

Authors: Isaac F Leach; Leonardo Belpassi; Paola Belanzoni; Remco W A Havenith; Johannes E M N Klein
Journal: Chemphyschem Date: 2021-05-28 Impact factor: 3.102

3. Direct synthesis of aryl-annulated [c]carbazoles by gold(i)-catalysed cascade reaction of azide-diynes and arenes.

Authors: Yuiki Kawada; Shunsuke Ohmura; Misaki Kobayashi; Wataru Nojo; Masaki Kondo; Yuka Matsuda; Junpei Matsuoka; Shinsuke Inuki; Shinya Oishi; Chao Wang; Tatsuo Saito; Masanobu Uchiyama; Takanori Suzuki; Hiroaki Ohno
Journal: Chem Sci Date: 2018-09-10 Impact factor: 9.825

C(sp³ )-H Bond Activation by Vinylidene Gold(I) Complexes: A Concerted Asynchronous or Stepwise Process?

1. Monoaurated vs. diaurated intermediates: causality or independence?

2. Efficient Computation of Geometries for Gold Complexes.

3. Direct synthesis of aryl-annulated [c]carbazoles by gold(i)-catalysed cascade reaction of azide-diynes and arenes.

Review 4. σ-Noninnocence: Masked Phenyl-Cation Transfer at Formal Ni^IV.

5. Cationic Gold(I) Diarylallenylidene Complexes: Bonding Features and Ligand Effects.

6. Epoxidation of Alkenes by Peracids: From Textbook Mechanisms to a Quantum Mechanically Derived Curly-Arrow Depiction.

7. cPCET versus HAT: A Direct Theoretical Method for Distinguishing X-H Bond-Activation Mechanisms.

8. The Pentagonal-Pyramidal Hexamethylbenzene Dication: Many Shades of Coordination Chemistry at Carbon.

Review 4. σ-Noninnocence: Masked Phenyl-Cation Transfer at Formal NiIV.

Review 4. σ-Noninnocence: Masked Phenyl-Cation Transfer at Formal Ni^IV.