A series of titanium amidinato complexes were synthesized by stoichiometric insertion reactions of carbodiimides into bis(π–η⁵:σ–η¹-pentafulvene)titanium complexes. NMR studies and single-crystal X-ray diffraction showed κ¹N coordination of the former carbodiimides to the metal center. DFT calculations were performed, confirming the clear preference for a single nitrogen atom coordinating to the metal center with a high energy transition state for the formation of a chelating heteroallyl ligand. Depending on the pentafulvene ligand, additional insertion reactions of carbodiimides into the remaining Ti–C_exo bond were observed. This allows for a stepwise insertion of the corresponding carbodiimides and offers the possibility to further functionalize the complexes. The reactivity of the remaining pentafulvene ligand is further demonstrated in reactions with H-acidic and multiple bond substrates.

中文翻译：

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碳二亚胺中钛 κ1N 酰胺配合物的合成、表征和功能化


通过碳二亚胺的化学计量插入反应η σ η π合成了一系列钛酰胺配合物NMR 研究和单晶 X 射线衍射显示，前碳二亚胺与金属中心发生 κ¹N 配位。进行了 DFT 计算，证实了对形成螯合异烯丙基配体的单个氮原子与具有高能过渡态的金属中心配位的明显偏好。根据五黄酮配体，观察到碳二亚胺向剩余的 Ti-C_外键中的额外插入反应。这允许逐步插入相应的碳二亚胺，并提供了进一步功能化复合物的可能性。剩余的五黄酮配体的反应性在与 H 酸和多键底物的反应中进一步证明。