The synthesis of novel asymmetrically substituted cobalt complexes of the type [Co(CO)(NO)(NHC)(PR₃)] (NHC = ⁱPr₂Im, PR₃ = PMe₃ (1), PEt₃(2), PHⁱPr₂ (3); PR₃ = PMe₃;, NHC = Me₂Im^Me (4), MeⁱPrIm (5), Me^tBuIm (6), ⁱPr₂Im^Me (7); R₂Im = 1,3-dialkylimidazolin-2-ylidene) is reported. These complexes are stabilized by N-heterocyclic carbene (NHC), phosphine, carbonyl, and nitrosyl ligands and have been synthesized from the reaction of a NHC-substituted precursor of the type [Co(CO)₂(NO)(NHC)] and the corresponding phosphine. The synthesis of [Co(CO)(NO)(Me^tBuIm)(PMe₃)] (6) and [Co(CO)(NO)(ⁱPr₂Im^Me)(PMe₃)] (7) proceeds in a thermal reaction even at room temperature by quantitative replacement of one carbonyl with a phosphine ligand. All of the other complexes were synthesized using photochemical conditions. Complexes 1–6 have been characterized by elemental analysis, IR spectroscopy, and multinuclear NMR spectroscopy and in some cases by X-ray crystallography. All complexes are volatile, are stable upon sublimation, and decompose readily in a stepwise manner at elevated temperature. The complex [Co(CO)(NO)(ⁱPr₂Im)(PMe₃)] (1) as well as cobalt complexes that were reported earlier, i.e. [Co(CO)(NO)(ⁱPr₂Im)₂], [Co(CO)(NO)(Me^tBuIm)₂], and [Co(CO)₂(NO)(ⁱPr₂Im)], are evaluated and have been successfully applied in the deposition of cobalt-based thin films.

中文翻译：

---

非对称取代的四面体钴NHC配合物及其作为ALD和低温CVD前体的用途

新型[Co（CO）（NO）（NHC）（PR ₃）]（NHC = ⁱ Pr ₂ Im，PR ₃ = PMe ₃（1），PEt ₃（2）， PH^我镨₂（3）; PR ₃ = PME ₃ ;，NHC =我₂林^我（4）中，Me^我PRIM（5）中，Me^吨BuIm（6），^我镨₂林^我（7）; 据报道R ₂ Im ＝ 1，3-二烷基咪唑啉-2-亚烷基。这些配合物由N-杂环卡宾（NHC），膦，羰基和亚硝酰基配体稳定，并且是由[Co（CO）₂（NO）（NHC）]型NHC取代的前体的反应合成的，相应的膦。[Co（CO）（NO）（Me ^t BuIm）（PMe ₃）]（6）和[Co（CO）（NO）（ⁱ Pr ₂ Im ^Me）（PMe ₃）]（7）的合成）甚至通过在室温下通过用膦配体定量取代一种羰基来进行热反应。使用光化学条件合成所有其他配合物。配合物1 - 6已经通过元素分析，红外光谱，和多核NMR光谱和在一些情况下通过X射线晶体学。所有的配合物都是挥发性的，在升华后是稳定的，并且在升高的温度下容易以逐步的方式分解。络合物[Co（CO）（NO）（ⁱ Pr ₂ Im）（PMe ₃）]（1）以及先前报道的钴络合物，即[Co（CO）（NO）（ⁱ Pr ₂ Im）₂]，[Co（CO）（NO）（Me ^t BuIm）₂ ]和[Co（CO）₂（NO）（ⁱ Pr ₂ Im）]进行了评估，并已成功应用于钴基沉积薄膜。