三碘化铱在 CD3OD 中的反应：Ir(III) 的还原、CD3-OD 键的断裂、Ir-D 酸的离解和烯烃反应。

Iridium porphyrins in CD3OD: reduction of Ir(III), CD3-OD bond cleavage, Ir-D acid dissociation and alkene reactions.

机构信息

Temple University, Department of Chemistry, 130 Beury Hall, 1901 North 13th Street, Philadelphia, Pennsylvania 19122, United States.

出版信息

Inorg Chem. 2013 Apr 15;52(8):4611-7. doi: 10.1021/ic400240b. Epub 2013 Mar 29.

DOI:10.1021/ic400240b

PMID:23540797

Abstract

Methanol solutions of iridium(III) tetra(p-sulfonatophenyl)porphyrin [(TSPP)Ir(III)] form an equilibrium distribution of methanol and methoxide complexes ((TSPP)Ir(III)(CD3OD)(2-n)(OCD3)n). Reaction of [(TSPP)Ir(III) with dihydrogen (D2) in methanol produces an iridium hydride (TSPP)Ir(III)-D(CD3OD) in equilibrium with an iridium(I) complex ((TSPP)Ir(I)(CD3OD)). The acid dissociation constant of the iridium hydride (Ir-D) in methanol at 298 K is 3.5 × 10(-12). The iridium(I) complex ((TSPP)Ir(I)(CD3OD)) catalyzes reaction of (TSPP)Ir(III)-D(CD3OD) with CD3-OD to produce an iridium methyl complex (TSPP)Ir(III)-CD3(CD3OD) and D2O. Reactions of the iridium hydride with ethene and propene produce iridium alkyl complexes, but the Ir-D complex fails to give observable addition with acetaldehyde and carbon monoxide in methanol. Reaction of the iridium hydride with propene forms both the isopropyl and propyl complexes with free energy changes (ΔG° 298 K) of -1.3 and -0.4 kcal mol(-1) respectively. Equilibrium thermodynamics and reactivity studies are used in discussing relative Ir-D, Ir-OCD3 and Ir-CD2- bond energetics in methanol.

摘要

甲醇溶液中的三(对磺基苯基)卟啉合铱(III) [(TSPP)Ir(III)] 形成甲醇和甲氧基络合物的平衡分布((TSPP)Ir(III)(CD3OD)(2-n)(OCD3)n)。[(TSPP)Ir(III)与甲醇中的氢气(D2)反应生成铱氢化物(TSPP)Ir(III)-D(CD3OD)，与铱(I)络合物((TSPP)Ir(I)(CD3OD))处于平衡状态。在 298 K 时，甲醇中铱氢化物(Ir-D)的酸离解常数为 3.5×10(-12)。铱(I)络合物((TSPP)Ir(I)(CD3OD))催化(TSPP)Ir(III)-D(CD3OD)与 CD3-OD 的反应，生成铱甲基络合物(TSPP)Ir(III)-CD3(CD3OD)和 D2O。铱氢化物与乙烯和丙烯的反应生成铱烷基络合物，但 Ir-D 络合物在甲醇中与乙醛和一氧化碳的反应未能观察到加成。铱氢化物与丙烯反应形成异丙基和丙基络合物，自由能变化(ΔG°298 K)分别为-1.3 和-0.4 kcal mol(-1)。通过平衡热力学和反应性研究，讨论了甲醇中相对的 Ir-D、Ir-OCD3 和 Ir-CD2-键的能量学。