Takao Toshiro, Matsuzawa Shinji, Nagaoka Masahiro
Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan.
Inorg Chem. 2024 Nov 18;63(46):22214-22226. doi: 10.1021/acs.inorgchem.4c03837. Epub 2024 Nov 7.
Heterometallic tetrahydrido complexes [CpRe(H)(μ-H)MCp] (: M = Ir, : M = Rh) were synthesized by the reaction of [CpReH] and [CpM(sol)] (M = Ir, Rh) followed by deprotonation. Although possesses four hydrides and adopts a 30-electron configuration as [CpRu(μ-H)RuCp] () does, the positions of the hydrides in differ from those in : two terminal and two bridging hydrides. In addition, adaptive natural density partitioning (AdNDP) analysis demonstrated that a direct Re-M bond is held in . Although cationic pentahydrido complexes [CpRe(H)(μ-H)MCp] (: M = Ir, : M = Rh) do not contain a direct Re-M bond, the formation of a Re-M bond in the intermediate of the hydride site exchange was also inferred by DFT calculations. DFT calculations suggested that the Re-M bond plays a crucial role in the site exchange of hydrides in and . While μ-phosphido complex [Cp*(PPh)Re(H)(μ-H)(μ-PPh)Ir(H)Cp*] () was obtained by the reaction of with PPh, the treatment of with PMe resulted in the formation of a 1:1 mixture of [CpRe(H)(PMe)] and [CpIr(H)PMe] via the rupture of the Re-Ir bond.
通过[CpReH]与[CpM(sol)]（M = Ir，Rh）反应然后去质子化，合成了异金属四氢化物配合物[CpRe(H)(μ-H)MCp]（M = Ir，M = Rh）。尽管[CpRe(H)(μ-H)MCp]拥有四个氢化物，并且像[CpRu(μ-H)RuCp]（[CpRu(μ-H)RuCp]）一样采用30电子构型，但[CpRe(H)(μ-H)MCp]中氢化物的位置与[CpRu(μ-H)RuCp]中的不同：两个端基氢化物和两个桥连氢化物。此外，自适应自然密度分区（AdNDP）分析表明[CpRe(H)(μ-H)MCp]中存在直接的Re-M键。尽管阳离子五氢化物配合物[CpRe(H)(μ-H)MCp]（M = Ir，M = Rh）不包含直接的Re-M键，但通过密度泛函理论（DFT）计算也推断出在氢化物位点交换中间体中形成了Re-M键。DFT计算表明，Re-M键在[CpRe(H)(μ-H)MCp]和[CpRe(H)(μ-H)MCp]的氢化物位点交换中起关键作用。当通过[CpRe(H)(μ-H)MCp]与PPh反应得到μ-磷化物配合物[Cp*(PPh)Re(H)(μ-H)(μ-PPh)Ir(H)Cp*]（[Cp*(PPh)Re(H)(μ-H)(μ-PPh)Ir(H)Cp*]）时，用PMe处理[Cp*(PPh)Re(H)(μ-H)(μ-PPh)Ir(H)Cp*]会导致通过Re-Ir键的断裂形成[CpRe(H)(PMe)]和[CpIr(H)PMe]的1:1混合物。
