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

29 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
DOIs
Publication statusPublished - 1999 Nov 8

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of '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)(PPh<sub>3</sub>)<sub>2</sub>". H/D exchange between CH<sub>3</sub> and DCl'. Together they form a unique fingerprint.

  • Cite this