Rütter Daniel, Nöthling Nils, Leutzsch Markus, Auer Alexander A, Fürstner Alois
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany.
J Am Chem Soc. 2025 Apr 23;147(16):13871-13884. doi: 10.1021/jacs.5c02178. Epub 2025 Apr 11.
Homodimeric complexes [XMo≡MoX] are commonplace, but in no case is the corresponding monomeric [MoX] species known; conversely, none of the very rare monomeric complexes [MoX] has the respective homodimeric analogue. This mutual exclusivity ends with the present study; on top, an entirely unprecedented class of heterodimers of type [XMo≡MoY] is reported. Key to success was the use of tripodal silanolates as ancillary ligands; the fence formed by properly chosen peripheral substituents shields the sensitive Mo(+3) center; homodimerization of the resulting [MoX] complexes is then kinetically strongly disfavored, though possible. The monomers are able to cleave NO and convert -dihalides into metal alkylidynes; they exist in different binding modes, in which the basal phenyl ring of the ligand backbone is either completely unengaged with the central metal or tightly bound to it, depending on whether the ligand sphere is complemented by solvent molecules or not. If the latter are sufficiently labile, a surprisingly facile heterodimerization of the d electron fragments will ensue; the resulting products [XMo≡MoY] incorporate the intact Cummins complex [(Bu)(Ar)N]Mo (Ar = 3,5-dimethylphenyl) as one of their constituents, which is famous for not engaging in metal-metal triple bonding otherwise. Heterodimerization was also observed with simple -butoxide ligands. The new type of heterodimers features unusually long yet robust Mo≡Mo bonds, which are notably polarized according to DFT. However, there is no direct correlation between the extreme Mo≡Mo bond lengths and the strikingly deshielded Mo NMR signals, since ligand-based orbitals can also markedly affect the shielding tensor.
同二聚体配合物[XMo≡MoX]很常见,但相应的单体[MoX]物种却从未被发现;相反,极为罕见的单体配合物[MoX]中没有一个具有各自的同二聚体类似物。本研究打破了这种相互排斥的情况;此外,还报道了一类全新的[XMo≡MoY]型异二聚体。成功的关键在于使用三脚架硅醇盐作为辅助配体;适当选择的外围取代基形成的“围栏”保护了敏感的Mo(+3)中心;尽管可能发生,但由此产生的[MoX]配合物的同二聚化在动力学上受到强烈抑制。这些单体能够裂解NO并将二卤化物转化为金属亚烷基;它们以不同的结合模式存在,其中配体主链的基底苯环要么与中心金属完全不结合,要么紧密结合,这取决于配体球是否被溶剂分子补充。如果后者足够不稳定,d电子片段将发生令人惊讶的容易的异二聚化;生成的产物[XMo≡MoY]包含完整的卡明斯配合物[(Bu)(Ar)N]Mo(Ar = 3,5 - 二甲基苯基)作为其成分之一,该配合物因否则不参与金属 - 金属三键而闻名。用简单的丁氧基配体也观察到了异二聚化。这种新型异二聚体具有异常长但稳定的Mo≡Mo键,根据密度泛函理论(DFT),这些键具有明显的极化。然而,极端的Mo≡Mo键长与显著去屏蔽的Mo NMR信号之间没有直接关联,因为基于配体的轨道也会显著影响屏蔽张量。