Substitution Reactions at [FeFe] Hydrogenase Models Containing [2Fe3S] Assembly by Phosphine or Phosphite Ligands
详细信息 查看全文
- 作者：Ahmad Q. Daraosheh ; Mohammad K. Harb ; Jochen Windhager ; Helmar Grls ; Mohammad El-khateeb ; Wolfgang Weigand
- 刊名：Organometallics
- 出版年：2009
- 出版时间：November 9, 2009
- 年：2009
- 卷：28
- 期：21
- 页码：6275-6280
- 全文大小：861K
- 年卷期：v.28,no.21(November 9, 2009)
- ISSN：1520-6041
文摘
In order to elucidate the role of the “on−off” coordination mode of the thioether group in the [2Fe3S] complex 1, which is related to the active site of [FeFe] hydrogenases, substitution studies of CO ligands by phosphite and phosphine ligands at compound Fe2(μ-S2(C3H6)2S-μ)(CO)5 (1) have been investigated. The reaction of 1 with 1 equiv of trimethylphosphite gave the kinetically controlled product Fe2(μ-S2(C3H6)2S)(CO)5P(OMe)3 (2) or the thermodynamically controlled product Fe2(μ-S2(C3H6)2S-μ)(CO)4P(OMe)3 (3) depending on the reaction conditions. Moreover, Fe2(μ-S2(C3H6)2S)(CO)4[P(OMe)3]2 (4) and Fe2(μ-S2(C3H6)2S)(CO)4(PMe3)2 (5) were obtained from the reactions of 1 with excess P(OMe)3 and excess PMe3, respectively. These novel complexes have been characterized by IR, 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray single-crystal structure analysis.