Tetranuclear Ni complexes were synthesized with bonding to BH, NR, and O in atypical surface-like geometries. The previously reported electron-deficient cluster [(ⁱPr₃P)Ni]₅H₆ (1) reacts with N-methylmorpholine oxide to give [(ⁱPr₃P)Ni]₄H₄(μ₄-O) (2), which contains O coordinated in the center of a square-plane arrangement of Ni atoms. Reaction of 1 with benzonitrile gave the square-planar tetranuclear Ni cluster [(ⁱPr₃P)Ni]₄H₄(μ₄-NCH₂Ph) (3), which contains an imido donor in a square-based-pyramidal geometry. This reaction also gives [(ⁱPr₃P)Ni(N≡CPh)]₃ (4), with bridging benzonitrile ligands. Trimer 4 was independently synthesized from the reaction of Ni(COD)₂, ⁱPr₃P, and PhC≡N. The addition of dihydrogen to a 1:1 mixture of [(ⁱPr₃P)₂Ni]₂(N₂) and (ⁱPr₃P)₂NiCl₂ yielded [(ⁱPr₃P)Ni]₄(μ₃-H)₄(μ₂-Cl)₂ (5), with a tetrahedral Ni core, in contrast to the square-planar geometries of 2 and 3. The solid-state structure of 5 was determined using both X-ray and neutron diffraction. Reaction of 5 with LiBH₄ gave [(ⁱPr₃P)Ni]₄H₄(μ₄-BH)₂] (6) via loss of LiCl and H₂.

中文翻译：

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表面模拟正方形平面四核镍氢集群和粘接的合成以μ ₄ -NR，-O和-BH配体

合成了四核镍配合物，其与BH，NR和O结合成非典型的表面状几何结构。先前报道的缺电子的簇[（^我镨₃ P）的Ni] ₅ ħ ₆（1同）反应Ñ甲基吗啉氧化物，得到[（^我镨₃ P）的Ni] ₄ ħ ₄（μ ₄ -O）（2），其中包含在Ni原子的方平面排列的中心协调的O. 1与苄腈的反应生成了方形方形四核Ni簇[[ ⁱ Pr ₃ P）Ni] ₄ H₄（μ ₄ -NCH ₂ PH）（3），其中包含在一个正方形的基于锥型几何酰亚胺供体。该反应还产生[（ⁱ Pr ₃ P）Ni（N ＝ CPh）] ₃（4），其具有桥联的苄腈配体。三聚体4是由Ni（COD）₂，ⁱ Pr ₃ P和PhC≡N的反应独立合成的。将二氢添加到[（ⁱ Pr ₃ P）₂ Ni] ₂（N ₂）和（ⁱ Pr ₃ P）₂的1：1混合物中的NiCl ₂，得到[（^我镨₃ P）的Ni] ₄（μ ₃ -H）₄（μ ₂ -Cl）₂（5），具有四面体的Ni芯，在对比的是正方形平面的几何形状的2和3。使用X射线和中子衍射法测定5的固态结构。的反应5与的LiBH ₄得到[（^我镨₃ P）的Ni] ₄ ħ ₄（μ ₄ -BH）₂ ]（6）通过LiCl和H的损失₂。