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

doi:10.1016/S0277-5387(98)00358-1

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

Department of Chemistry

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

9 Citations (Scopus)

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 language	English
Pages (from-to)	811-815
Number of pages	5
Journal	Polyhedron
Volume	18
Issue number	6
DOIs	https://doi.org/10.1016/S0277-5387(98)00358-1
Publication status	Published - 1999 Jan 22

Bibliographical note

Funding Information:
We wish to thank the Korea Science and Engineering Foundation (Grant No. 97-05-01-05-01-3) and the Korean Ministry of Education (Grant No. BSRI-97-3412) for their financial supports of this study.

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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@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",

note = "Funding Information: We wish to thank the Korea Science and Engineering Foundation (Grant No. 97-05-01-05-01-3) and the Korean Ministry of Education (Grant No. BSRI-97-3412) for their financial supports of this study. ",

year = "1999",

month = jan,

day = "22",

doi = "10.1016/S0277-5387(98)00358-1",

language = "English",

volume = "18",

pages = "811--815",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Limited",

number = "6",

}

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 journal › Article › peer-review

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

N1 - Funding Information: We wish to thank the Korea Science and Engineering Foundation (Grant No. 97-05-01-05-01-3) and the Korean Ministry of Education (Grant No. BSRI-97-3412) for their financial supports of this study.

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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U2 - 10.1016/S0277-5387(98)00358-1

DO - 10.1016/S0277-5387(98)00358-1

M3 - Article

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VL - 18

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EP - 815

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

IS - 6

ER -