An Arbuzov-type reaction with the bis(alkynyl) iridium complex [Cp∗Ir(L)(CCAr)2]

Yongjia Li; Rakesh Ganguly; Weng Kee Leong

doi:10.1016/j.jorganchem.2016.05.018

An Arbuzov-type reaction with the bis(alkynyl) iridium complex [Cp∗Ir(L)(CCAr)₂]

Yongjia Li, Rakesh Ganguly, Weng Kee Leong^*

^*Corresponding author for this work

Nanyang Technological University

Research output: Contribution to journal › Article › peer-review

7 Citations (Scopus)

Abstract

The bis(alkynyl) iridium complexes [Cp∗Ir(L)(CCAr)₂] undergo an Arbuzov-type reaction with phosphites to give four-membered iridacyclic phosphonates [Cp∗Ir(L){C(Ar)=C[P(=O)(OR)₂]C=CHAr}]. These can isomerise to a five-membered iridafuran in the presence of a strong acid. In the absence of a phosphite, the bis(alkynyl) iridium complexes undergo acid-catalysed aerobic oxidation to form 1,2-diketone iridabenzofurans [Cp∗Ir(L){C₆H₄-1,2-CH=CC(=O)C(=O)Ar}]. A common reaction pathway involving initial protonation and alkynyl migration is proposed.

Original language	English
Pages (from-to)	42-47
Number of pages	6
Journal	Journal of Organometallic Chemistry
Volume	818
DOIs	https://doi.org/10.1016/j.jorganchem.2016.05.018
Publication status	Published - Sept 1 2016
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2016 Elsevier B.V.

ASJC Scopus Subject Areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Keywords

Acid catalysis
Arbuzov
bis(alkynyl)
Iridacycle
Iridium
Oxidation

Access to Document

10.1016/j.jorganchem.2016.05.018

Cite this

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title = "An Arbuzov-type reaction with the bis(alkynyl) iridium complex [Cp∗Ir(L)(CCAr)2]",

abstract = "The bis(alkynyl) iridium complexes [Cp∗Ir(L)(CCAr)2] undergo an Arbuzov-type reaction with phosphites to give four-membered iridacyclic phosphonates [Cp∗Ir(L){C(Ar)=C[P(=O)(OR)2]C=CHAr}]. These can isomerise to a five-membered iridafuran in the presence of a strong acid. In the absence of a phosphite, the bis(alkynyl) iridium complexes undergo acid-catalysed aerobic oxidation to form 1,2-diketone iridabenzofurans [Cp∗Ir(L){C6H4-1,2-CH=CC(=O)C(=O)Ar}]. A common reaction pathway involving initial protonation and alkynyl migration is proposed.",

keywords = "Acid catalysis, Arbuzov, bis(alkynyl), Iridacycle, Iridium, Oxidation",

author = "Yongjia Li and Rakesh Ganguly and Leong, {Weng Kee}",

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year = "2016",

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doi = "10.1016/j.jorganchem.2016.05.018",

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T1 - An Arbuzov-type reaction with the bis(alkynyl) iridium complex [Cp∗Ir(L)(CCAr)2]

AU - Li, Yongjia

AU - Ganguly, Rakesh

AU - Leong, Weng Kee

PY - 2016/9/1

Y1 - 2016/9/1

N2 - The bis(alkynyl) iridium complexes [Cp∗Ir(L)(CCAr)2] undergo an Arbuzov-type reaction with phosphites to give four-membered iridacyclic phosphonates [Cp∗Ir(L){C(Ar)=C[P(=O)(OR)2]C=CHAr}]. These can isomerise to a five-membered iridafuran in the presence of a strong acid. In the absence of a phosphite, the bis(alkynyl) iridium complexes undergo acid-catalysed aerobic oxidation to form 1,2-diketone iridabenzofurans [Cp∗Ir(L){C6H4-1,2-CH=CC(=O)C(=O)Ar}]. A common reaction pathway involving initial protonation and alkynyl migration is proposed.

AB - The bis(alkynyl) iridium complexes [Cp∗Ir(L)(CCAr)2] undergo an Arbuzov-type reaction with phosphites to give four-membered iridacyclic phosphonates [Cp∗Ir(L){C(Ar)=C[P(=O)(OR)2]C=CHAr}]. These can isomerise to a five-membered iridafuran in the presence of a strong acid. In the absence of a phosphite, the bis(alkynyl) iridium complexes undergo acid-catalysed aerobic oxidation to form 1,2-diketone iridabenzofurans [Cp∗Ir(L){C6H4-1,2-CH=CC(=O)C(=O)Ar}]. A common reaction pathway involving initial protonation and alkynyl migration is proposed.

KW - Acid catalysis

KW - Arbuzov

KW - bis(alkynyl)

KW - Iridacycle

KW - Iridium

KW - Oxidation

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