Formation and isomerization of cis, cis-Ir(H)2( - Ph)(CO)(PPh3)2 and cis, cis-Ir(H)( - Ph)2(CO)(PPh3)2 in oxidative addition of hydrogen and phenylacetylene to trans-Ir(CO)( - Ph)(PPh3)2

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

Research output: Contribution to journalArticle

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Abstract

Oxidative addition of H-R (H - Ph and H2) to trans-Ir( - Ph)(CO)(PPh3)2 (2) gives the initial products, cis, cis-Ir(H)( - Ph)2(CO)(PPh3)2 (3a) and cis, cis-Ir(H)2( - Ph)(CO)(PPh3)2 (3b), respectively. Both cis-bis(PPh3) complexes, 3a and 3b undergo isomerization to give the trans-bis(PPh3) complexes, trans, trans-Ir(H)( - Ph)2(CO)(PPh3)2 (4a) and cis, trans-Ir(H)2( - Ph)(CO)(PPh3)2 (4b). The isomerization, 3b→4b is first order with respect to 3b with k1=6.37×10-4 s-1 at 25°C under N2 in CDCl3. The reaction rate (k1) seems independent of the concentration of H2. A large negative entropy of activation (ΔS=-24.9±5.7 cal deg-1 mol-1) and a relatively small enthalpy of activation (ΔH=14.5±3.3 kcal mol-1) were obtained in the temperature range 15~35°C for the isomerization, 3b→4b under 1 atm of H2.

Original languageEnglish
Pages (from-to)811-815
Number of pages5
JournalPolyhedron
Volume18
Issue number6
DOIs
Publication statusPublished - 1999 Jan 22

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Carbon Monoxide
Isomerization
isomerization
Hydrogen
hydrogen
Chemical activation
Reaction rates
Enthalpy
Entropy
activation
phenylacetylene
reaction kinetics
enthalpy
entropy
Temperature
products

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

@article{fdc143abc12946fc972ec70e8715a073,
title = "Formation and isomerization of cis, cis-Ir(H)2( - Ph)(CO)(PPh3)2 and cis, cis-Ir(H)( - Ph)2(CO)(PPh3)2 in oxidative addition of hydrogen and phenylacetylene to trans-Ir(CO)( - Ph)(PPh3)2",
abstract = "Oxidative addition of H-R (H - Ph and H2) to trans-Ir( - Ph)(CO)(PPh3)2 (2) gives the initial products, cis, cis-Ir(H)( - Ph)2(CO)(PPh3)2 (3a) and cis, cis-Ir(H)2( - Ph)(CO)(PPh3)2 (3b), respectively. Both cis-bis(PPh3) complexes, 3a and 3b undergo isomerization to give the trans-bis(PPh3) complexes, trans, trans-Ir(H)( - Ph)2(CO)(PPh3)2 (4a) and cis, trans-Ir(H)2( - Ph)(CO)(PPh3)2 (4b). The isomerization, 3b→4b is first order with respect to 3b with k1=6.37×10-4 s-1 at 25°C under N2 in CDCl3. The reaction rate (k1) seems independent of the concentration of H2. A large negative entropy of activation (ΔS≠=-24.9±5.7 cal deg-1 mol-1) and a relatively small enthalpy of activation (ΔH≠=14.5±3.3 kcal mol-1) were obtained in the temperature range 15~35°C for the isomerization, 3b→4b under 1 atm of H2.",
author = "{Shik Chin}, Chong and Moonhyun Oh and Gyongshik Won and Haeyeon Cho and Dongchan Shin",
year = "1999",
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doi = "10.1016/S0277-5387(98)00358-1",
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volume = "18",
pages = "811--815",
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Formation and isomerization of cis, cis-Ir(H)2( - Ph)(CO)(PPh3)2 and cis, cis-Ir(H)( - Ph)2(CO)(PPh3)2 in oxidative addition of hydrogen and phenylacetylene to trans-Ir(CO)( - Ph)(PPh3)2. / Shik Chin, Chong; Oh, Moonhyun; Won, Gyongshik; Cho, Haeyeon; Shin, Dongchan.

In: Polyhedron, Vol. 18, No. 6, 22.01.1999, p. 811-815.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Formation and isomerization of cis, cis-Ir(H)2( - Ph)(CO)(PPh3)2 and cis, cis-Ir(H)( - Ph)2(CO)(PPh3)2 in oxidative addition of hydrogen and phenylacetylene to trans-Ir(CO)( - Ph)(PPh3)2

AU - Shik Chin, Chong

AU - Oh, Moonhyun

AU - Won, Gyongshik

AU - Cho, Haeyeon

AU - Shin, Dongchan

PY - 1999/1/22

Y1 - 1999/1/22

N2 - Oxidative addition of H-R (H - Ph and H2) to trans-Ir( - Ph)(CO)(PPh3)2 (2) gives the initial products, cis, cis-Ir(H)( - Ph)2(CO)(PPh3)2 (3a) and cis, cis-Ir(H)2( - Ph)(CO)(PPh3)2 (3b), respectively. Both cis-bis(PPh3) complexes, 3a and 3b undergo isomerization to give the trans-bis(PPh3) complexes, trans, trans-Ir(H)( - Ph)2(CO)(PPh3)2 (4a) and cis, trans-Ir(H)2( - Ph)(CO)(PPh3)2 (4b). The isomerization, 3b→4b is first order with respect to 3b with k1=6.37×10-4 s-1 at 25°C under N2 in CDCl3. The reaction rate (k1) seems independent of the concentration of H2. A large negative entropy of activation (ΔS≠=-24.9±5.7 cal deg-1 mol-1) and a relatively small enthalpy of activation (ΔH≠=14.5±3.3 kcal mol-1) were obtained in the temperature range 15~35°C for the isomerization, 3b→4b under 1 atm of H2.

AB - Oxidative addition of H-R (H - Ph and H2) to trans-Ir( - Ph)(CO)(PPh3)2 (2) gives the initial products, cis, cis-Ir(H)( - Ph)2(CO)(PPh3)2 (3a) and cis, cis-Ir(H)2( - Ph)(CO)(PPh3)2 (3b), respectively. Both cis-bis(PPh3) complexes, 3a and 3b undergo isomerization to give the trans-bis(PPh3) complexes, trans, trans-Ir(H)( - Ph)2(CO)(PPh3)2 (4a) and cis, trans-Ir(H)2( - Ph)(CO)(PPh3)2 (4b). The isomerization, 3b→4b is first order with respect to 3b with k1=6.37×10-4 s-1 at 25°C under N2 in CDCl3. The reaction rate (k1) seems independent of the concentration of H2. A large negative entropy of activation (ΔS≠=-24.9±5.7 cal deg-1 mol-1) and a relatively small enthalpy of activation (ΔH≠=14.5±3.3 kcal mol-1) were obtained in the temperature range 15~35°C for the isomerization, 3b→4b under 1 atm of H2.

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VL - 18

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EP - 815

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

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