Selective deprotonation and decarbonylation from hydridocarbonyl- iridium(III) compounds with trimethylamine N-oxide

Chong Shik Chin, Moonhyun Oh, Gyongshik Won, Haeyeon Cho, Dongchan Shin

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Me3NO selectively abstracts the proton from [IrH(CO)(PPh3)2L(A)]0,1+,2+ (1) (A: -CCPh, Cl-, CH3CN and L: CH3CN, Cl-, ClO4/-) to give the trans-elimination products, Ir(CO)(PPh3)2(A) (2). The reductive elimination of H+ and Cl- from Ir(H)Cl2(CO)(PPh3)2 (1b) to give IrCl(CO)(PPh3)2 (2b) is first order in both 1b and Me3NO. The rate law d[2b]/dt=k(obs)[1b]=k2[1b][Me3NO] suggests the formation of (PPh3)2(Cl)2(CO)Ir-H-ON+Me3 in the rate determining step (k2) followed by the fast dissociation of both H-ON+Me3 and the trans ligand Cl-. The rate significantly varies with the cis ligand A and the trans ligand L and is slower with both A and L being Cl- than other ligands. Me3NO selectively eliminates CO from [Ir(H)2(CO)(PPh3)2L]0,+ (3) (L=CH3CN, ClO4/-) to produce [Ir(H)2(PPh3)2L'(CH3CN)]+ (4) (L'=CH3CN, PPh3) in the presence of L. Me3NO does not readily remove either H+ or CO from cis, trans- and trans, trans-Ir(H)(- CCPh)2(CO)(PPh3)2 and cis, trans-Ir(H)2Cl(CO)(PPh3)2. The choice whether hydridocarbonyls, 1 and 3 undergo the deprotonation or decarbonylation may be understood mostly in terms of thermodynamic stability of the products and partly by kinetic preference of Me3NO on proton and CO.

Original languageEnglish
Pages (from-to)85-88
Number of pages4
JournalBulletin of the Korean Chemical Society
Volume20
Issue number1
Publication statusPublished - 1999 Jan 20

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Iridium
Deprotonation
Carbon Monoxide
Ligands
Protons
trimethyloxamine
Thermodynamic stability

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

@article{e2f0405d996246d5898a60553272da67,
title = "Selective deprotonation and decarbonylation from hydridocarbonyl- iridium(III) compounds with trimethylamine N-oxide",
abstract = "Me3NO selectively abstracts the proton from [IrH(CO)(PPh3)2L(A)]0,1+,2+ (1) (A: -CCPh, Cl-, CH3CN and L: CH3CN, Cl-, ClO4/-) to give the trans-elimination products, Ir(CO)(PPh3)2(A) (2). The reductive elimination of H+ and Cl- from Ir(H)Cl2(CO)(PPh3)2 (1b) to give IrCl(CO)(PPh3)2 (2b) is first order in both 1b and Me3NO. The rate law d[2b]/dt=k(obs)[1b]=k2[1b][Me3NO] suggests the formation of (PPh3)2(Cl)2(CO)Ir-H-ON+Me3 in the rate determining step (k2) followed by the fast dissociation of both H-ON+Me3 and the trans ligand Cl-. The rate significantly varies with the cis ligand A and the trans ligand L and is slower with both A and L being Cl- than other ligands. Me3NO selectively eliminates CO from [Ir(H)2(CO)(PPh3)2L]0,+ (3) (L=CH3CN, ClO4/-) to produce [Ir(H)2(PPh3)2L'(CH3CN)]+ (4) (L'=CH3CN, PPh3) in the presence of L. Me3NO does not readily remove either H+ or CO from cis, trans- and trans, trans-Ir(H)(- CCPh)2(CO)(PPh3)2 and cis, trans-Ir(H)2Cl(CO)(PPh3)2. The choice whether hydridocarbonyls, 1 and 3 undergo the deprotonation or decarbonylation may be understood mostly in terms of thermodynamic stability of the products and partly by kinetic preference of Me3NO on proton and CO.",
author = "Chin, {Chong Shik} and Moonhyun Oh and Gyongshik Won and Haeyeon Cho and Dongchan Shin",
year = "1999",
month = "1",
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Selective deprotonation and decarbonylation from hydridocarbonyl- iridium(III) compounds with trimethylamine N-oxide. / Chin, Chong Shik; Oh, Moonhyun; Won, Gyongshik; Cho, Haeyeon; Shin, Dongchan.

In: Bulletin of the Korean Chemical Society, Vol. 20, No. 1, 20.01.1999, p. 85-88.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Selective deprotonation and decarbonylation from hydridocarbonyl- iridium(III) compounds with trimethylamine N-oxide

AU - Chin, Chong Shik

AU - Oh, Moonhyun

AU - Won, Gyongshik

AU - Cho, Haeyeon

AU - Shin, Dongchan

PY - 1999/1/20

Y1 - 1999/1/20

N2 - Me3NO selectively abstracts the proton from [IrH(CO)(PPh3)2L(A)]0,1+,2+ (1) (A: -CCPh, Cl-, CH3CN and L: CH3CN, Cl-, ClO4/-) to give the trans-elimination products, Ir(CO)(PPh3)2(A) (2). The reductive elimination of H+ and Cl- from Ir(H)Cl2(CO)(PPh3)2 (1b) to give IrCl(CO)(PPh3)2 (2b) is first order in both 1b and Me3NO. The rate law d[2b]/dt=k(obs)[1b]=k2[1b][Me3NO] suggests the formation of (PPh3)2(Cl)2(CO)Ir-H-ON+Me3 in the rate determining step (k2) followed by the fast dissociation of both H-ON+Me3 and the trans ligand Cl-. The rate significantly varies with the cis ligand A and the trans ligand L and is slower with both A and L being Cl- than other ligands. Me3NO selectively eliminates CO from [Ir(H)2(CO)(PPh3)2L]0,+ (3) (L=CH3CN, ClO4/-) to produce [Ir(H)2(PPh3)2L'(CH3CN)]+ (4) (L'=CH3CN, PPh3) in the presence of L. Me3NO does not readily remove either H+ or CO from cis, trans- and trans, trans-Ir(H)(- CCPh)2(CO)(PPh3)2 and cis, trans-Ir(H)2Cl(CO)(PPh3)2. The choice whether hydridocarbonyls, 1 and 3 undergo the deprotonation or decarbonylation may be understood mostly in terms of thermodynamic stability of the products and partly by kinetic preference of Me3NO on proton and CO.

AB - Me3NO selectively abstracts the proton from [IrH(CO)(PPh3)2L(A)]0,1+,2+ (1) (A: -CCPh, Cl-, CH3CN and L: CH3CN, Cl-, ClO4/-) to give the trans-elimination products, Ir(CO)(PPh3)2(A) (2). The reductive elimination of H+ and Cl- from Ir(H)Cl2(CO)(PPh3)2 (1b) to give IrCl(CO)(PPh3)2 (2b) is first order in both 1b and Me3NO. The rate law d[2b]/dt=k(obs)[1b]=k2[1b][Me3NO] suggests the formation of (PPh3)2(Cl)2(CO)Ir-H-ON+Me3 in the rate determining step (k2) followed by the fast dissociation of both H-ON+Me3 and the trans ligand Cl-. The rate significantly varies with the cis ligand A and the trans ligand L and is slower with both A and L being Cl- than other ligands. Me3NO selectively eliminates CO from [Ir(H)2(CO)(PPh3)2L]0,+ (3) (L=CH3CN, ClO4/-) to produce [Ir(H)2(PPh3)2L'(CH3CN)]+ (4) (L'=CH3CN, PPh3) in the presence of L. Me3NO does not readily remove either H+ or CO from cis, trans- and trans, trans-Ir(H)(- CCPh)2(CO)(PPh3)2 and cis, trans-Ir(H)2Cl(CO)(PPh3)2. The choice whether hydridocarbonyls, 1 and 3 undergo the deprotonation or decarbonylation may be understood mostly in terms of thermodynamic stability of the products and partly by kinetic preference of Me3NO on proton and CO.

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