Bond Forming Reactions on Iridium Centers (Chemistry)

本文提出的研究在催化领域具有重要意义。这项工作的成果将有助于合成燃料领域的发展。建议用反式-RIR(CO)LL，R=烷基或烷氧基，L=磷给体的络合物来考察成键反应。这些16电子正方形平面络合物很容易加入分子，使碳和氢、氧和氢、碳和碳以及氧和碳键进入Ir上的顺式位置。在许多情况下，可以观察到还原消除反应中键的形成。例如通过向反式RIR(CO)L添加二氢、HX或金属氢化物来形成C-H和O-H键，C-C键的形成是通过将一些烷基卤化物和酸性氯化物加到反式RIR(CO)L1(R=烷基)上进行的，而C-O键的形成是通过向反式RIR(CO)L1加成酸性氯化物和醛来实现的。这一提议的独特之处在于能够从类似的络合物中研究不同的成键反应。这种系统的研究可以使人们更好地理解还原消除反应形成键的机理。

The research proposed has significance in the area of catalysis. The results of this work will aid in the development of the synthetic fuels area. It is proposed to use the complexes, trans-RIr(CO)LL,R = alkyl or alkoxy and L = phosphorus donor, to examine bond forming reactions. These sixteen-electron square planar complexes readily add molecules bringing carbon and hydrogen, oxygen and hydrogen, carbon and carbon, and oxygen and carbon bonds into cis positions on the iridium. In many cases the formation of bonds in a reductive elimination reaction is observed. For instance C-H and O-H bond formation occur by addition of dihydrogen, HX or metal hydrides to trans RIr(CO)L, C-C bond formation occurs by addition of some alkyl halides and acid chlorides to trans RIr(CO)LL (R=alkyl) and C-O bond formation occurs by addition of acid chlorides and aldehydes to trans ROIr(CO)LL. The unique feature of this proposal is the ability to study different bond forming reactions from analogous complexes. Such a systematic investigation may allow a greater understanding of the mechanisms of bond formation by reductive elimination reactions.