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

doi:10.1021/om9903442

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

Department of Chemistry

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

5 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 language	English
Pages (from-to)	4810-4816
Number of pages	7
Journal	Organometallics
Volume	18
Issue number	23
DOIs	https://doi.org/10.1021/om9903442
Publication status	Published - 1999 Nov 8

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@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 = nov,

day = "8",

doi = "10.1021/om9903442",

language = "English",

volume = "18",

pages = "4810--4816",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "23",

}

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

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

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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