The reactions of the MeCN-substituted compounds [Re₂(CO)₉(NCMe)] and [H₃Re₃(CO)₁₁(NCMe)] with SbPh₃ are described. Treatment of [Re₂(CO)₉(NCMe)] with SbPh₃ in refluxing benzene furnished [Re₂(CO)₉(SbPh₃)] (1) in good yield. Complex 1 reacts with SbPh₃ in the presence of Me₃NO in acetonitrile to give [Re₂(CO)₈(σ-C₆H₅)(µ-SbPh₂)(NCMe)] (2), which on further reaction with additional SbPh₃ in refluxing benzene afforded the known complex [Re₂(CO)₈(σ-C₆H₅)(µ-SbPh₂)(SbPh₃)] (3). Heating 1 with SbPh₃ at 110 °C yields 3, which on prolonged heating at 110 °C in the presence of SbPh₃ furnished the known stibene-bridged compound [Re₂(CO)₇(µ-SbPh₂)₂(SbPh₃)] (4). Complex 2 is a rare example of a dirhenium complex containing a sigma-bonded phenyl group and a labile acetonitrile ligand in the same molecule. The stibene-bridged dirhenium complexes (2−4) result from the cleavage of antimony-carbon and Re–Re bonds. Heating [H₃Re₃(CO)₁₁(NCMe)] with SbPh₃ in refluxing toluene afforded the new compounds [H₃Re₃(CO)₁₁(SbPh₃)] (5), [H₂Re₃(CO)₁₁(µ-SbPh₂)(SbPh₃)] (6), and [HRe₂(CO)₆(µ-SbPh₂)(SbPh₃)₂] (8) together with previously reported compound [HRe₂(CO)₇(µ-SbPh₂)(SbPh₃)] (7). Compound 5 is a simple monosubstituted product, while 6 contains a terminally coordinated SbPh₃ ligand and a bridging SbPh₂ group formed by Sb–Ph bond scission. Compound 8 results from cluster fragmentation and SbPh₃ ligand activation by Sb–Ph bond cleavage. A series of separate thermolysis experiments have been performed in order to establish the relationship between the different products. Compounds 1, 2, 5, 6, and 8 have been structurally characterized by X-ray crystallography. The bonding in these new compounds has been investigated by electronic structure calculations.

描述了 MeCN 取代的化合物 [Re ₂ (CO) ₉ (NCMe)] 和 [H ₃ Re ₃ (CO) ₁₁ (NCMe)] 与 SbPh ₃的反应。在回流苯中用SbPh ₃处理[Re ₂ (CO) ₉ (NCMe)]，以良好的收率提供[Re ₂ (CO) ₉ (SbPh ₃ )] (1)。在乙腈中存在 Me ₃ NO的情况下，配合物 1 与 SbPh ₃反应生成[Re ₂ (CO) ₈ (σ-C ₆ H ₅ )(μ-SbPh ₂)(NCMe)] (2)，在回流苯中与额外的 SbPh ₃进一步反应得到已知的复合物 [Re ₂ (CO) ₈ (σ-C ₆ H ₅ )(µ-SbPh ₂ )(SbPh ₃ )] (3). 在 110 °C 下用 SbPh ₃加热 1产生 3，在 SbPh ₃存在下在 110 °C 下长时间加热提供已知的二苯桥化合物 [Re ₂ (CO) ₇ (µ-SbPh ₂ ) ₂ (SbPh _{3 )})] (4). 配合物 2 是二铼配合物的一个罕见例子，在同一分子中含有一个 σ 键合的苯基和一个不稳定的乙腈配体。锑-碳和 Re-Re 键的裂解产生了锑桥连二铼配合物 (2-4)。在回流的甲苯中用 SbPh ₃加热 [H ₃ Re ₃ (CO) ₁₁ (NCMe)]得到新化合物 [H ₃ Re ₃ (CO) ₁₁ (SbPh ₃ )] (5), [H ₂ Re ₃ (CO) ₁₁ (µ-SbPh ₂ )(SbPh ₃ )] (6) 和 [HRe ₂ (CO) ₆ (µ-SbPh ₂)(SbPh ₃ ) ₂ ] (8) 连同先前报道的化合物 [HRe ₂ (CO) ₇ (μ-SbPh ₂ )(SbPh ₃ )] (7)。化合物 5 是一个简单的单取代产物，而 6 包含一个末端配位的 SbPh ₃配体和一个由 Sb-Ph 键断裂形成的桥连 SbPh ₂基团。化合物 8 来自簇断裂和 SbPh ₃通过 Sb-Ph 键裂解激活配体。为了建立不同产品之间的关系，已经进行了一系列单独的热解实验。化合物 1、2、5、6 和 8 已通过 X 射线晶体学进行结构表征。已经通过电子结构计算研究了这些新化合物中的键合。