A new pyridine functionalized N-heterocyclic silane with ambident reactivity as a ligand has been synthesized and characterized by NMR spectroscopy (¹H, ¹³C{¹H}, ²⁹Si), mass spectrometry, elemental analysis, and X-ray crystallography. This ligand reacts with iridium and rhodium cod precursors (cod = 1,5-cyclooctadiene) to yield two new complexes that possess divergent, and unexpected, binding properties. In particular, no oxidative addition occurs at the intraligand Si-H unit. With the iridium(I) center, the ligand acts as a tertiary amino-pyridine chelator, whereas coordination of rhodium(I) to the ligand occurs with arene π-complexation on an opposite side. The latter interaction yields an unprecedented, electronically induced, coordination change at the silicon center over a long spatial distance. The new iridium and rhodium compounds are of high interest as they provide two potentially different reactions sites in one complex and as these sorts of complexes are known to activate small molecules like dihydrogen or silanes. Hence, the compounds are promising candidates for applications in tandem catalysis. Furthermore, the rhodium complex might be utilized for molecular switches, sensors, and comparable applications.

中文翻译：

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吡啶和铑的吡啶官能化N杂环硅烷配合物–配位的意外变化

合成了一种新型的吡啶官能化的N-杂环硅烷，具有作为配体的环境反应性，并通过NMR光谱进行了表征（¹ H，¹³ C { ¹ H}，²⁹Si），质谱，元素分析和X射线晶体学。该配体与铱和铑的鳕鱼前体（鳕鱼= 1,5-环辛二烯）反应，生成两种具有发散的和出乎意料的结合特性的新配合物。特别地，在配体内Si-H单元上没有发生氧化加成。在铱（I）中心，配体充当叔氨基吡啶螯合剂，而铑（I）与配体的配位则通过芳烃π络合物在另一侧发生。后者的相互作用在较长的空间距离上在硅中心产生了前所未有的，电子感应的配位变化。新的铱和铑化合物备受关注，因为它们在一个配合物中提供两个可能不同的反应位点，并且已知这类配合物可激活小分子，如二氢或硅烷。因此，该化合物是用于串联催化的有希望的候选物。此外，铑配合物可用于分子开关，传感器和类似应用。