The dinitrogen donor N,N’-diisopropylformamidine [PrⁱN=C(H)NHPrⁱ] reacts with the triosmium cluster Os₃(CO)₁₀(NCMe)₂ at room temperature to yield the isomeric clusters HOs₃(CO)₉[μ-C(O)NPrⁱC(H)NPrⁱ] (1) and HOs₃(CO)₁₀[μ-NPrⁱC(H)NPrⁱ] (2) in a 1:2.8 ratio. 1 contains an edge-bridging iminocarbamoyl ligand, while 2 contains a bridging formamidinate ligand. Thermolysis of 1 yields 2 plus the face-capped cluster HOs₃(CO)₉[μ₃-NPrⁱC(H)NPrⁱ] (3). The decarbonylation of 2 to 3 + CO confirms the molecularity of the observed reaction steps. The three products have been fully characterized in solution by IR and NMR spectroscopies, and the solid-state structures for 1-3 have been determined by X-ray crystallography. The kinetics for the thermolysis reaction were investigated over the temperature range 342–383 K, and the concentration versus time profiles for the conversion of 1 → 2 → 3 + CO have been successfully modeled using two consecutive, irreversible first-order reactions. The bonding in clusters 1-3 have been examined by DFT, and these data support cluster 1 as the kinetic substitution product and cluster 2 as the thermodynamically favored isomer.

二氮供体N，N'-二异丙基甲am [Pr ⁱ N = C（H）NHPr ⁱ ]在室温下与tri簇Os ₃（CO）₁₀（NCMe）₂反应，得到异构簇HOs ₃（CO）₉ [μ-C（O）NPR^我C（H）NPR^我]（1）和的HO ₃（CO）₁₀ [μ-NPR^我C（H）NPR^我]（2）以1：2.8的比例。1包含边缘桥接的亚氨基甲酰氨基配体，而2包含桥接的甲酰胺基配体。热解1产率2加上面封端的簇的HO ₃（CO）₉ [μ ₃ -nPr^我C（H）NPR^我]（3）。2至3  + CO的脱羰反应证实了所观察到的反应步骤的分子性。三种产品已充分表征在通过IR和NMR光谱，和固态结构的解决方案1 - 3已经通过X射线晶体学确定。在342–383 K的温度范围内研究了热解反应的动力学，以及浓度与时间的关系曲线，用于1  →  2的转化 →  已使用两个连续的，不可逆的一阶反应成功模拟了3 + CO。在群集的结合1 - 3已经由DFT检查，并且这些数据支持簇1作为动能取代产物和簇2作为热力学有利的异构体。