Phosphane- and Phosphite-Substituted Diiron Diselenolato Complexes as Models for [FeFe]-Hydrogenases†
Phosphane- and Phosphite-Substituted Diiron Diselenolato Complexes as Models for [FeFe]-Hydrogenases†
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DOI：
10.1002/ejic.200900252
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发表时间：
2009-08
影响因子：
2.3
通讯作者：
Mohammad K. Harb;Jochen Windhager;Ahmad Q. Daraosheh;H. Görls;L. T. Lockett;N. Okumura;Dennis H. Evans;R. Glass;D. Lichtenberger;M. El‐khateeb;W. Weigand
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文献类型：
--
作者：
Mohammad K. Harb;Jochen Windhager;Ahmad Q. Daraosheh;H. Görls;L. T. Lockett;N. Okumura;Dennis H. Evans;R. Glass;D. Lichtenberger;M. El‐khateeb;W. Weigand
研究了三苯基膦、亚磷酸三甲酯和二(二苯基膦)乙烷(DPPE)配体对Fe2(μ-Se2 C3H，5 CH3)(CO)6(1)中末端CO配体的取代作用。治疗1与1当量。合成了Fe2(μ-Se2C3H5CH3)(CO)5(PPh3)(2)。1与过量的P(OMe)3在甲苯中回流反应，得到单取代和双取代亚磷酸根配合物Fe2(μSe2C3H5CH3)(CO)S P(OMe)3(3)和Fe2(g-Se2C3H5CH3)(CO)4-[P(OMe)3]2(4)。相反，1与1当量的反应。在Me3NO·2H2 0存在下，生成Fe2(μ-SeZC3H5CH3)(CO)4(κ2-Dppe)(5)和[Fe2(μ-Se2 C3H5CH3)(CO)5]2(μ-Dppe)(6)的混合物。新合成的配合物2-6经IR、1H、13C、77Se{1H}和31P{1H}核磁共振波谱、质谱学、元素分析和X-射线衍射谱确证。络合物2已被证明是弱酸--醋酸的电化学还原生成分子氢的催化剂。
The displacement of terminal CO ligands in Fe 2 (μ-Se 2 C 3 H, 5 CH 3 )(CO) 6 (1) by triphenylphosphane, trimethyl phosphite, and bis(diphenylphosphanyl)ethane (dppe) ligands is investigated. Treatment of 1 with 1 equiv. of triphenylphosphane afforded Fe 2 (μ-Se 2 C 3 H 5 CH 3 )(CO) 5 (PPh 3 ) (2). The mono- and disubstituted phosphite complexes Fe 2 (μSe 2 C 3 H 5 CH 3 )(CO) S P(OMe) 3 (3)andFe 2 (g-Se 2 C 3 H 5 CH 3 )(CO) 4 -[P(OMe) 3 ] 2 (4) were obtained from the reaction of 1 with excess P(OMe) 3 at reflux in toluene. In contrast, the reaction of 1 with 1 equiv. of dppe in the presence of Me 3 NO·2H 2 0 gave a mixture of Fe 2 (μ-Se z C 3 H 5 CH 3 )(CO) 4 (κ 2 -dppe) (5) and [Fe 2 (μ-Se 2 C 3 H 5 CH 3 )(CO) 5 ] 2 (μ-dppe) (6). The newly synthesized complexes 2-6 were fully characterized by IR, 1 H NMR, 13 C NMR , 77 Se{ 1 H} NMR, and 31 P{ 1 H} NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray diffraction analysis. Complex 2 has proved to be a catalyst for the electrochemical reduction of the weak acid, acetic acid, to give molecular hydrogen.