The reaction of equimolar amounts of [Co(CO)3(NO)] and [PPN]CN, PPN+ = (PPh3)2N+, in THF at room temperature resulted in ligand substitution of a carbonyl towards the cyanido ligand presumably affording the complex salt PPN[Co(CO)2(NO)(CN)] as a reactive intermediate species which could not be isolated. Applying the synthetic protocol using the nitrosyl carbonyl in excess, the title reaction afforded unexpectedly the novel complex salt PPN[Co2(μ‐CN)(CO)4(NO)2] (1) in high yield. Because of many disorder phenomena in crystals of 1 the corresponding NBu4+ salt of 1 has been prepared and the molecular structure of the dinuclear metal core in NnBu4[Co2(μ‐CN)(CO)4(NO)2] (2) was determined by X‐ray crystal diffraction in a more satisfactory manner. In contrast to the former result, the reaction of [PPN]SCN with [Co(CO)3(NO)] yielded the mononuclear complex salt PPN[Co(CO)2(NO)(SCN‐κN)] (3) in good yield whose molecular structure in the solid was even determined and its composition additionally confirmed by spectroscopic means.

中文翻译：

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氰化物和硫氰酸盐对亚硝基羰基 [Co(CO)3 (NO)] 的反应性

等摩尔量的 [Co(CO)3(NO)] 和 [PPN]CN，PPN+ = (PPh3)2N+，在室温下在 THF 中的反应导致配体取代羰基朝向氰基配体，推测提供了配盐PPN[Co(CO)2(NO)(CN)]作为无法分离的活性中间体。应用使用过量亚硝酰基羰基的合成方案，标题反应出人意料地以高产率提供了新型复合盐 PPN[Co2(μ-CN)(CO)4(NO)2] (1)。由于 1 的晶体中存在许多无序现象，因此制备了 1 的相应 NBu4+ 盐，并确定了 NnBu4[Co2(μ-CN)(CO)4(NO)2] (2) 中双核金属核的分子结构通过 X 射线晶体衍射以更令人满意的方式。与之前的结果相反，