TY  - JOUR
AU  - Niu, Shuqiang
AU  - Strout, D.L.
AU  - Zarić, Snežana D.
AU  - Bayse, C.A.
AU  - Hall, Michael B.
PY  - 1999
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/63
AB  - The oxidative-addition/reductive-elimination (OA/RE) reactions of methane, ethylene and acetylene with the CpIr(PH3)(CH3)+ complex are investigated by ab initio methods and density functional theory (DFT). The calculated results shows that the OA reaction from CpIr(PH3)(CH3)(agostic-alkane)+ to CpIr(PH3)(CH3)(H)(alkyl)+ is endothermic by 4.4 and 0.8 kcal/mol with a low barrier of 11.5 and 10.0 kcal/mol at the DFT-B3LYP and coupled cluster with singles and doubles (CCSD) levels of theory, respectively. The RE reaction from CpIr(PH3)(CH3)(H)(alkyl)+ to a β-agostic complex, CpIr(PH3)(alkyl)+, is exothermic with a low barrier of 7.1 and 9.2 kcal/mol. A strong stabilizing interaction between either ethylene or acetylene and CpIr(PH3)(CH3)+ leads to a high activation barrier (24-36 kcal/mol) for the OA processes of either one. Compared to ethylene, the OA/RE reaction of acetylene with CpIr(PH3)(CH3)+ complex is more favorable. Thus, the dimerization of terminal alkynes catalyzed by cationic iridium complexes is plausible.
T2  - ACS Symposium Series / American Chemical Society
T1  - Theoretical studies of inorganic and organometallic reaction mechanisms 13: Methane, ethylene, and acetylene activation at a Cationic Iridium Center
VL  - 721
SP  - 138
EP  - 150
UR  - https://hdl.handle.net/21.15107/rcub_cherry_63
ER  - 

@article{
author = "Niu, Shuqiang and Strout, D.L. and Zarić, Snežana D. and Bayse, C.A. and Hall, Michael B.",
year = "1999",
abstract = "The oxidative-addition/reductive-elimination (OA/RE) reactions of methane, ethylene and acetylene with the CpIr(PH3)(CH3)+ complex are investigated by ab initio methods and density functional theory (DFT). The calculated results shows that the OA reaction from CpIr(PH3)(CH3)(agostic-alkane)+ to CpIr(PH3)(CH3)(H)(alkyl)+ is endothermic by 4.4 and 0.8 kcal/mol with a low barrier of 11.5 and 10.0 kcal/mol at the DFT-B3LYP and coupled cluster with singles and doubles (CCSD) levels of theory, respectively. The RE reaction from CpIr(PH3)(CH3)(H)(alkyl)+ to a β-agostic complex, CpIr(PH3)(alkyl)+, is exothermic with a low barrier of 7.1 and 9.2 kcal/mol. A strong stabilizing interaction between either ethylene or acetylene and CpIr(PH3)(CH3)+ leads to a high activation barrier (24-36 kcal/mol) for the OA processes of either one. Compared to ethylene, the OA/RE reaction of acetylene with CpIr(PH3)(CH3)+ complex is more favorable. Thus, the dimerization of terminal alkynes catalyzed by cationic iridium complexes is plausible.",
journal = "ACS Symposium Series / American Chemical Society",
title = "Theoretical studies of inorganic and organometallic reaction mechanisms 13: Methane, ethylene, and acetylene activation at a Cationic Iridium Center",
volume = "721",
pages = "138-150",
url = "https://hdl.handle.net/21.15107/rcub_cherry_63"
}

Niu, S., Strout, D.L., Zarić, S. D., Bayse, C.A.,& Hall, M. B.. (1999). Theoretical studies of inorganic and organometallic reaction mechanisms 13: Methane, ethylene, and acetylene activation at a Cationic Iridium Center. in ACS Symposium Series / American Chemical Society, 721, 138-150.
https://hdl.handle.net/21.15107/rcub_cherry_63

Niu S, Strout D, Zarić SD, Bayse C, Hall MB. Theoretical studies of inorganic and organometallic reaction mechanisms 13: Methane, ethylene, and acetylene activation at a Cationic Iridium Center. in ACS Symposium Series / American Chemical Society. 1999;721:138-150.
https://hdl.handle.net/21.15107/rcub_cherry_63 .

Niu, Shuqiang, Strout, D.L., Zarić, Snežana D., Bayse, C.A., Hall, Michael B., "Theoretical studies of inorganic and organometallic reaction mechanisms 13: Methane, ethylene, and acetylene activation at a Cationic Iridium Center" in ACS Symposium Series / American Chemical Society, 721 (1999):138-150,
https://hdl.handle.net/21.15107/rcub_cherry_63 .