State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116012, P. R. China.
Dalton Trans. 2012 Aug 28;41(32):9700-7. doi: 10.1039/c2dt30468f. Epub 2012 Jul 11.
Coordination of the pyridyl-attached diiron azadithiolate hexacarbonyl complexes (2 and 3) through the pyridyl nitrogen to the Re on 10-phenanthroline rhenium (5a) and 2,9-diphenyl-1,10-phenanthroline rhenium (5b) forms novel [Re-Fe] complexes 7a, 7b and 8 respectively. Under visible light illumination using triethylamine as a sacrificial electron donor and [Re-Fe] type complexes (7a, 7b or 8) as catalysts, remarkably increased efficiency was observed for photoinduced hydrogen production with a turnover number reaching 11.8 from complex 7a and 8.75 from 7b. To the best of our knowledge, these are the best values compared to other [Re-Fe] photocatalysts reported so far. In contrast to the parent molecules, the turnover number by the intermolecular combination of complexes 6a and 2 showed a value of 5.23, and that from 6b and 2 is 3.8, while no H(2) was detected from 8a and 3 under the same experimental conditions. Obviously, the intramolecular combination of rhenium(I) and [2Fe2S] as a catalyst is promising for efficient H(2) evolution, and it is better than the intermolecular multi-component system.
通过吡啶氮原子与钌上的 10-菲咯啉钌（5a）和 2,9-二苯基-1,10-菲咯啉钌（5b）的配位，将吡啶键合的二铁氮杂二硫代六羰基配合物（2 和 3）协调在一起，分别形成了新型[Re-Fe]配合物 7a、7b 和 8。在可见光照射下，使用三乙胺作为牺牲电子供体，[Re-Fe]型配合物（7a、7b 或 8）作为催化剂，观察到光诱导氢气产生的效率显著提高，配合物 7a 的周转数达到 11.8，配合物 7b 的周转数达到 8.75。据我们所知，与迄今为止报道的其他[Re-Fe]光催化剂相比，这些是最好的值。与母体分子相比，配合物 6a 和 2 的分子间组合的周转数为 5.23，配合物 6b 和 2 的周转数为 3.8，而在相同的实验条件下，配合物 8a 和 3 没有检测到 H2。显然，作为催化剂的[Re]和[2Fe2S]的分子内组合对于有效的 H2 演化是有希望的，并且优于分子间多组分系统。
