Reaction of an (alkyl)(alkenyl)(alkynyl)iridium(III) complex with HCl: Intramolecular C-C bond formation from alkyl, alkenyl, and alkynyl groups coordinated to "Ir(CO)(PPh3)2". H/D exchange between CH3 and DCl

Chong Shik Chin, Haeyeon Cho, Gyongshik Won, Moonhyun Oh, Kang Min Ok

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

Reaction of the (alkyl)(alkenyl)(alkynyl)iridium(III) complex [Ir(CH3)(CH=CHNEt3)(C≡ C(p-C6H4CH3))(CO)(PPh3) 2]ClO4 (3) with aqueous HCl initiates an intramolecular coupling reaction between -CH3 and -C≡C(p-C6H4CH3) groups to give [Ir(C(CH3)=CH(p-C6H4CH 3)-(CH=CHNEt3)(Cl)(CO)(PPh3) 2]ClO4 (5), which further reacts with aqueous HCl to produce [Ir(CH=CHNEt3)(Cl)2(CO)(PPh3) 2]ClO4 (6) and cis-CH3CH=CH(p-C6H4CH3) (7). Complex 5 yields the C-C coupling product [(p-C6H4CH3)HC=C(CH3)CH=CHNEt 3]ClO4 (8) when it is refluxed in CHCl3. The (alkyl)bis(alkynyl)iridium(III) compound Ir(CH3)(C≡C(p-C6H4CH3)) 2-(CO)(PPh3)2 (4) reacts with aqueous HCl to give H2C=C=CH(p-C6H4CH3) (9). Complex 3 reacts with excess DCl to give the d5 isotopomer CD3CD=CD(p-C6H4CH3) (7-d5), while the reaction of 4 with DCl gives the d1 isotopomer H2C=C=CD(p-C6H4CH3) (9-d1). Plausible reaction pathways are discussed for the formation of 7 and 9 and for the H/D exchange to give the isotopomer 7-d5.

Original languageEnglish
Pages (from-to)4810-4816
Number of pages7
JournalOrganometallics
Volume18
Issue number23
Publication statusPublished - 1999 Nov 8

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Iridium
Carbon Monoxide
iridium
methylidyne
Iridium compounds
iridium compounds
perchlorate
products

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

@article{97962ae71a6841a9a4cf84e393aa7878,
title = "Reaction of an (alkyl)(alkenyl)(alkynyl)iridium(III) complex with HCl: Intramolecular C-C bond formation from alkyl, alkenyl, and alkynyl groups coordinated to {"}Ir(CO)(PPh3)2{"}. H/D exchange between CH3 and DCl",
abstract = "Reaction of the (alkyl)(alkenyl)(alkynyl)iridium(III) complex [Ir(CH3)(CH=CHNEt3)(C≡ C(p-C6H4CH3))(CO)(PPh3) 2]ClO4 (3) with aqueous HCl initiates an intramolecular coupling reaction between -CH3 and -C≡C(p-C6H4CH3) groups to give [Ir(C(CH3)=CH(p-C6H4CH 3)-(CH=CHNEt3)(Cl)(CO)(PPh3) 2]ClO4 (5), which further reacts with aqueous HCl to produce [Ir(CH=CHNEt3)(Cl)2(CO)(PPh3) 2]ClO4 (6) and cis-CH3CH=CH(p-C6H4CH3) (7). Complex 5 yields the C-C coupling product [(p-C6H4CH3)HC=C(CH3)CH=CHNEt 3]ClO4 (8) when it is refluxed in CHCl3. The (alkyl)bis(alkynyl)iridium(III) compound Ir(CH3)(C≡C(p-C6H4CH3)) 2-(CO)(PPh3)2 (4) reacts with aqueous HCl to give H2C=C=CH(p-C6H4CH3) (9). Complex 3 reacts with excess DCl to give the d5 isotopomer CD3CD=CD(p-C6H4CH3) (7-d5), while the reaction of 4 with DCl gives the d1 isotopomer H2C=C=CD(p-C6H4CH3) (9-d1). Plausible reaction pathways are discussed for the formation of 7 and 9 and for the H/D exchange to give the isotopomer 7-d5.",
author = "Chin, {Chong Shik} and Haeyeon Cho and Gyongshik Won and Moonhyun Oh and Ok, {Kang Min}",
year = "1999",
month = "11",
day = "8",
language = "English",
volume = "18",
pages = "4810--4816",
journal = "Organometallics",
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publisher = "American Chemical Society",
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}

Reaction of an (alkyl)(alkenyl)(alkynyl)iridium(III) complex with HCl : Intramolecular C-C bond formation from alkyl, alkenyl, and alkynyl groups coordinated to "Ir(CO)(PPh3)2". H/D exchange between CH3 and DCl. / Chin, Chong Shik; Cho, Haeyeon; Won, Gyongshik; Oh, Moonhyun; Ok, Kang Min.

In: Organometallics, Vol. 18, No. 23, 08.11.1999, p. 4810-4816.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Reaction of an (alkyl)(alkenyl)(alkynyl)iridium(III) complex with HCl

T2 - Intramolecular C-C bond formation from alkyl, alkenyl, and alkynyl groups coordinated to "Ir(CO)(PPh3)2". H/D exchange between CH3 and DCl

AU - Chin, Chong Shik

AU - Cho, Haeyeon

AU - Won, Gyongshik

AU - Oh, Moonhyun

AU - Ok, Kang Min

PY - 1999/11/8

Y1 - 1999/11/8

N2 - Reaction of the (alkyl)(alkenyl)(alkynyl)iridium(III) complex [Ir(CH3)(CH=CHNEt3)(C≡ C(p-C6H4CH3))(CO)(PPh3) 2]ClO4 (3) with aqueous HCl initiates an intramolecular coupling reaction between -CH3 and -C≡C(p-C6H4CH3) groups to give [Ir(C(CH3)=CH(p-C6H4CH 3)-(CH=CHNEt3)(Cl)(CO)(PPh3) 2]ClO4 (5), which further reacts with aqueous HCl to produce [Ir(CH=CHNEt3)(Cl)2(CO)(PPh3) 2]ClO4 (6) and cis-CH3CH=CH(p-C6H4CH3) (7). Complex 5 yields the C-C coupling product [(p-C6H4CH3)HC=C(CH3)CH=CHNEt 3]ClO4 (8) when it is refluxed in CHCl3. The (alkyl)bis(alkynyl)iridium(III) compound Ir(CH3)(C≡C(p-C6H4CH3)) 2-(CO)(PPh3)2 (4) reacts with aqueous HCl to give H2C=C=CH(p-C6H4CH3) (9). Complex 3 reacts with excess DCl to give the d5 isotopomer CD3CD=CD(p-C6H4CH3) (7-d5), while the reaction of 4 with DCl gives the d1 isotopomer H2C=C=CD(p-C6H4CH3) (9-d1). Plausible reaction pathways are discussed for the formation of 7 and 9 and for the H/D exchange to give the isotopomer 7-d5.

AB - Reaction of the (alkyl)(alkenyl)(alkynyl)iridium(III) complex [Ir(CH3)(CH=CHNEt3)(C≡ C(p-C6H4CH3))(CO)(PPh3) 2]ClO4 (3) with aqueous HCl initiates an intramolecular coupling reaction between -CH3 and -C≡C(p-C6H4CH3) groups to give [Ir(C(CH3)=CH(p-C6H4CH 3)-(CH=CHNEt3)(Cl)(CO)(PPh3) 2]ClO4 (5), which further reacts with aqueous HCl to produce [Ir(CH=CHNEt3)(Cl)2(CO)(PPh3) 2]ClO4 (6) and cis-CH3CH=CH(p-C6H4CH3) (7). Complex 5 yields the C-C coupling product [(p-C6H4CH3)HC=C(CH3)CH=CHNEt 3]ClO4 (8) when it is refluxed in CHCl3. The (alkyl)bis(alkynyl)iridium(III) compound Ir(CH3)(C≡C(p-C6H4CH3)) 2-(CO)(PPh3)2 (4) reacts with aqueous HCl to give H2C=C=CH(p-C6H4CH3) (9). Complex 3 reacts with excess DCl to give the d5 isotopomer CD3CD=CD(p-C6H4CH3) (7-d5), while the reaction of 4 with DCl gives the d1 isotopomer H2C=C=CD(p-C6H4CH3) (9-d1). Plausible reaction pathways are discussed for the formation of 7 and 9 and for the H/D exchange to give the isotopomer 7-d5.

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