The reaction of one and two equivalents of the N‐heterocyclic carbene IMes [IMes = 1,3‐bis(2,4,6‐trimethyl‐phenyl)imidazolin‐2‐ylidene] or the cyclic (alkyl)(amino)carbene cAAC^Me [cAAC^Me = 1‐(2,6‐diisopropyl‐phenyl)‐3,3,5,5‐tetra‐methylpyrrolidin‐2‐ylidene] with [TiCl₄] in n‐hexane results in the formation of mono‐ and bis‐carbene complexes [TiCl₄(IMes)] 1, [TiCl₄(IMes)₂] 2, [TiCl₄(cAAC^Me)] 3, and [TiCl₄(cAAC^Me)₂] 4, respectively. For comparison, the titanium(IV) NHC complex [TiCl₄(IiPr^Me)] 5 (IiPr^Me = 1,3‐diisopropyl‐4,5‐dimethyl‐imidazolin‐2‐ylidene) has been synthesized and structurally characterized. The reaction of [TiCl₄(IMes)] 1 with PMe₃ affords the mixed substituted complex [TiCl₄(IMes)(PMe₃)] 6. The reactions of [TiCl₃(THF)₃] with two equivalents of the carbenes IMes and cAAC^Me in n‐hexane lead to the clean formation of the titanium(III) complexes [TiCl₃(IMes)₂] 7 and [TiCl₃(cAAC^Me)₂] 8. Compounds 1–8 have been completely characterized by elemental analysis, IR and multinuclear NMR spectroscopy and for 2–5, 7 and 8 by X‐ray diffraction. Magnetometry in solution, EPR and UV/Vis spectroscopy and DFT calculations performed on 7 and 8 are indicative of a predominantly metal‐centered d¹‐radical in both cases.

中文翻译：

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钛（IV）和钛（III）的N-杂环碳烯和环状（烷基）（氨基）卡宾配合物

一和两当量的N杂环卡宾IMes [IMes = 1,3-双（2,4,6-三甲基苯基）咪唑啉-2-亚烷基]或环状（烷基）（氨基）卡宾cAAC的反应^我[CAAC^我= 1-（2,6-二异丙基苯基）-3,3,5,5-四甲基吡咯烷-2-亚基]与[的TiCl ₄ ]在ñ在单-的形成-己烷的结果和双卡宾络合物[TiCl ₄（IMes）] 1，[TiCl ₄（IMes）₂ ] 2，[TiCl ₄（cAAC ^Me）] 3和[TiCl ₄（cAAC ^Me）₂ ]分别为4。为了进行比较，已经合成了钛（IV）NHC复合物[TiCl ₄（I i Pr ^Me）] 5（I i Pr ^Me = 1,3-二异丙基-4,5-二甲基咪唑啉-2-亚基）。表征。[TiCl ₄（IMes）] 1与PMe ₃反应，得到混合的取代配合物[TiCl ₄（IMes）（PMe ₃）] 6。[TiCl ₃（THF）₃ ]与两当量的羧甲基IMes和cAAC ^Me在n中的反应正己烷会导致钛（III）络合物[TiCl ₃（IMes）₂ ] 7和[TiCl ₃（cAAC ^Me）₂ ] 8的干净形成。化合物1 - 8已经完全通过元素分析，IR和多核NMR谱和2 - 5，7和8通过X射线衍射。在两种情况下，溶液中的磁力计，EPR和UV / Vis光谱以及对7和8进行的DFT计算都表明主要以金属为中心的d ¹自由基。