Abstract
Ab initio electronic structure calculations are used to study substituent effects in Vaska-type complexes, trans-IrL2(CO)X (1-X) (X = F, Cl, Br, I, CN, H, CH3, SiH3, OH, and SH; L = PH3). Both the electron affinity and the ionization potential of 1-X are computed to increase upon descending the halogen series of complexes, which indicates, surprisingly, that the complexes with more electronegative halogens are more difficult to reduce and easier to oxidize. The computed electron affinity trend is consistent with the half-wave reduction potential trend known for 1-X (L = PPh3; X = F, Cl, Br, and I). Computed carbonyl stretch frequencies for 1-X are greater than experimental values (L = PPh3), but observed trends are well reproduced. The redox and spectroscopic trends are discussed in terms of the substituent effects on the electronic structure of 1-X, particularly as revealed in the molecular orbital energy level diagrams of these complexes. The reaction energy for H2 addition to 1-X, leading to the cis,trans-(H)2IrL2(CO)X (2-X) product, has been computed. After electron correlation effects are included (MP4(SDTQ)), the reaction enthalpy computed for 1-Cl is -18.4 kcal/mol (L = PH3) as compared to a reported experimental value of -14 kcal/mol (L = PPh3). Compared with available experimental data, the electronic effects of L (L = PH3, NH3, or AsH3) and X on the thermodynamics of the H2 addition reaction are accurately reproduced by the model calculations at all levels of theory (HF and MPn). Formation of the hypothetical products cis,trans- and trans,trans-(H)2IrL2(CO)X (2-X and 3-X) (X = BH2, NH2, and PH2) is used to demonstrate that π-acceptor substituents promote the H2 addition reaction to 1-X while π-donor substituents disfavor addition.
| Original language | English |
|---|---|
| Pages (from-to) | 5122-5130 |
| Number of pages | 9 |
| Journal | Inorganic Chemistry |
| Volume | 33 |
| Issue number | 22 |
| Publication status | Published - 1994 |
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- Inorganic Chemistry
Cite this
Ab initio molecular orbital study of substituent effects in Vaska type complexes (trans-IrL2(CO)X) : Electron affinities, ionization potentials, carbonyl stretch frequencies, and the thermodynamics of H2 dissociative addition. / Abu-Hasanayn, Faraj; Goldman, Alan S; Krogh-Jespersen, Karsten.
In: Inorganic Chemistry, Vol. 33, No. 22, 1994, p. 5122-5130.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Ab initio molecular orbital study of substituent effects in Vaska type complexes (trans-IrL2(CO)X)
T2 - Electron affinities, ionization potentials, carbonyl stretch frequencies, and the thermodynamics of H2 dissociative addition
AU - Abu-Hasanayn, Faraj
AU - Goldman, Alan S
AU - Krogh-Jespersen, Karsten
PY - 1994
Y1 - 1994
N2 - Ab initio electronic structure calculations are used to study substituent effects in Vaska-type complexes, trans-IrL2(CO)X (1-X) (X = F, Cl, Br, I, CN, H, CH3, SiH3, OH, and SH; L = PH3). Both the electron affinity and the ionization potential of 1-X are computed to increase upon descending the halogen series of complexes, which indicates, surprisingly, that the complexes with more electronegative halogens are more difficult to reduce and easier to oxidize. The computed electron affinity trend is consistent with the half-wave reduction potential trend known for 1-X (L = PPh3; X = F, Cl, Br, and I). Computed carbonyl stretch frequencies for 1-X are greater than experimental values (L = PPh3), but observed trends are well reproduced. The redox and spectroscopic trends are discussed in terms of the substituent effects on the electronic structure of 1-X, particularly as revealed in the molecular orbital energy level diagrams of these complexes. The reaction energy for H2 addition to 1-X, leading to the cis,trans-(H)2IrL2(CO)X (2-X) product, has been computed. After electron correlation effects are included (MP4(SDTQ)), the reaction enthalpy computed for 1-Cl is -18.4 kcal/mol (L = PH3) as compared to a reported experimental value of -14 kcal/mol (L = PPh3). Compared with available experimental data, the electronic effects of L (L = PH3, NH3, or AsH3) and X on the thermodynamics of the H2 addition reaction are accurately reproduced by the model calculations at all levels of theory (HF and MPn). Formation of the hypothetical products cis,trans- and trans,trans-(H)2IrL2(CO)X (2-X and 3-X) (X = BH2, NH2, and PH2) is used to demonstrate that π-acceptor substituents promote the H2 addition reaction to 1-X while π-donor substituents disfavor addition.
AB - Ab initio electronic structure calculations are used to study substituent effects in Vaska-type complexes, trans-IrL2(CO)X (1-X) (X = F, Cl, Br, I, CN, H, CH3, SiH3, OH, and SH; L = PH3). Both the electron affinity and the ionization potential of 1-X are computed to increase upon descending the halogen series of complexes, which indicates, surprisingly, that the complexes with more electronegative halogens are more difficult to reduce and easier to oxidize. The computed electron affinity trend is consistent with the half-wave reduction potential trend known for 1-X (L = PPh3; X = F, Cl, Br, and I). Computed carbonyl stretch frequencies for 1-X are greater than experimental values (L = PPh3), but observed trends are well reproduced. The redox and spectroscopic trends are discussed in terms of the substituent effects on the electronic structure of 1-X, particularly as revealed in the molecular orbital energy level diagrams of these complexes. The reaction energy for H2 addition to 1-X, leading to the cis,trans-(H)2IrL2(CO)X (2-X) product, has been computed. After electron correlation effects are included (MP4(SDTQ)), the reaction enthalpy computed for 1-Cl is -18.4 kcal/mol (L = PH3) as compared to a reported experimental value of -14 kcal/mol (L = PPh3). Compared with available experimental data, the electronic effects of L (L = PH3, NH3, or AsH3) and X on the thermodynamics of the H2 addition reaction are accurately reproduced by the model calculations at all levels of theory (HF and MPn). Formation of the hypothetical products cis,trans- and trans,trans-(H)2IrL2(CO)X (2-X and 3-X) (X = BH2, NH2, and PH2) is used to demonstrate that π-acceptor substituents promote the H2 addition reaction to 1-X while π-donor substituents disfavor addition.
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M3 - Article
VL - 33
SP - 5122
EP - 5130
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 22
ER -