Cooperative B−H bond activation reactions with thio‐ and iminophosphoryl tethered ruthenium‐carbene complexes are reported. The complexes show surprisingly different reactivities towards the commonly employed boranes CatBH, PinBH and BH₃⋅LB as a result of different modes of metal–ligand cooperation. Although the iminophosphoryl system allows for selective 1,2‐addition of the B−H bond across the Ru=C double bond, the sulfur analogue only delivers the 1,2‐addition product for CatBH, whereas activation of BH₃ and PinBH lead to further insertion reactions in one or more sides of the Ru‐C‐P‐S‐ring. The different reactivities can be explained by the differences in the electronics of the carbene complexes and the phosphoryl tether and by the Lewis acidities of the boranes. DFT calculations show that the mechanism of the reactions either proceeds by an addition across the Ru=C bond with different regioselectivities or across the Ru−S linkage.

中文翻译：

---

钌碳化合物配合物中B-H键活化反应的多功能模式：加成，开环和插入

据报道，与硫代和亚氨基磷酰基系的钌-卡宾配合物发生的合作式B-H键活化反应。的配合物表现出对通常使用的硼烷CatBH，PinBH和BH出奇不同反应性的₃ ⋅LB作为金属-配体合作的不同模式的结果。尽管亚氨基磷酰基系统允许通过Ru = C双键选择性地将B-H键进行1,2-加成，但硫类似物仅提供CatBH的1,2-加成产物，而活化BH ₃和PinBH会导致在Ru‐C‐P‐S‐ring的一侧或多侧进一步插入反应。卡宾配合物和磷酰系链的电子学差异以及硼烷的路易斯酸度可以解释不同的反应性。DFT计算表明，反应机理要么通过具有不同区域选择性的Ru = C键或Ru-S键的加成而进行。