Experiments to gain mechanistic insight into catalytic H/D exchange of unactivated arenes by [(ⁱPr₃P)Ni]₅H₆ (1) are described. The reaction order with respect to 1, arene substrate, and added ⁱPr₃P were determined, as well as the temperature dependence of reaction rate. Site-selectivity data were obtained by monitoring the reaction of 1 with fluorobenzene and 2-methoxynaphthalene. H/D exchange competition reactions between arenes reacted with 1 were performed. The addition of an excess of Hg to a solution of 1 provided the new heterometallic cluster [(ⁱPr₃P)Ni]₅H₆(μ₄-Hg) (2); this species also undergoes H/D exchange with C₆D₆, albeit more slowly than 1. Reaction of cluster 1 with TlCp (Cp = C₅H₅) gave (η⁵-Cp)Ni[(ⁱPr₃P)Ni]₄(μ₂-H)₄(μ₄-Tl) (3) with the loss of H₂. A similar transfer of cyclopentadienyl to Ni occurred when 1 was reacted with MgCp₂, to give (η⁵-Cp)Ni[(ⁱPr₃P)Ni]₄H₆(μ₄-MgCp) (4), but not H₂ loss. Reaction of 1 with cyclopentadiene gave the 5-coordinate hydride complex (η⁵-Cp)Ni[(ⁱPr₃P)Ni]₄(μ₂-H)₄(μ₅-H) (5). The Cp* analogue, (η⁵-Cp*)Ni[(ⁱPr₃P)Ni]₄(μ₂-H)₄(μ₅-H) (6) (where Cp* = C₅Me₅), was synthesized by reacting 1 with LiCp* in THF, or by reaction of 1 with pentamethylcyclopentadiene.

中文翻译：

---

五核Ni-H团簇对H / D交换的机械观察以及潜在中间体的结构类似物的合成和表征

描述了通过机械手段了解未活化的芳烃通过[[ ⁱ Pr ₃ P）Ni] ₅ H ₆（1）进行催化H / D交换的实验。相对于该反应，以1，芳烃底物，并加入^我镨₃ P含量确定的，以及反应速率的温度依赖性。通过监测1与氟苯和2-甲氧基萘的反应获得位点选择性数据。在与1起反应的芳烃之间进行H / D交换竞争反应。在1的溶液中添加过量的Hg提供了新的杂金属簇[[^我镨₃ P）的Ni] ₅ ħ ₆（μ ₄ -Hg）（ 2）; 该物种也与C ₆ D ₆进行了H / D交换，尽管速度比1慢。簇的反应1与TLCP（CP = C ₅ H ^ ₅），得到（η ⁵ -Cp）的Ni [（^我镨₃ P）的Ni] ₄（μ ₂ -H） ₄（μ ₄ -Tl）（ 3）与所述H _2的损失。当1出现类似的环戊二烯基向Ni的转移用MGCP反应₂，得到（η ⁵ -Cp）的Ni [（^我镨₃ P）的Ni] ₄ ħ ₆（μ ₄ -MgCp）（4），但不为H _2个损失。的反应1与环戊二烯，得到5-坐标氢化物络合物（η ⁵ -Cp）的Ni [（^我镨₃ P）的Ni] ₄（μ ₂ -H）₄（μ ₅ -H）（5）。在CP *类似物，（η ⁵ -Cp *）的Ni [（^我镨₃ P）的Ni] ₄（μ ₂ -H）₄（μ ₅ -H）（6）（其中Cp * = C ₅我₅），通过反应而合成1用LICP *在THF中，或通过反应1用五甲基环戊二烯。