de Azevedo Santos Lucas, Wagner Timon, Visscher Klaas, Nitsch Jörn, Bickelhaupt F Matthias, Fonseca Guerra Célia
Department of Chemistry and Pharmaceutical Sciences, AIMMS, Vrije Universiteit Amsterdam, De Boelelaan 1108, 1081 HZ Amsterdam, The Netherlands.
Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
Phys Chem Chem Phys. 2024 Aug 7;26(31):20928-20936. doi: 10.1039/d4cp00250d.
We have quantum chemically analyzed the closed-shell d-d metallophilic interaction in dimers of square planar [M(CO)X] complexes (M = Ni, Pd, Pt; X = Cl, Br, I) using dispersion-corrected density functional theory at ZORA-BLYP-D3(BJ)/TZ2P level of theory. Our purpose is to reveal the nature of the [X(CO)M]⋯[M(CO)X] bonding mechanism by analyzing trends upon variations in M and X. Our analyses reveal that the formation of the [M(CO)X] dimers is favored by an increasingly stabilizing electrostatic interaction when the M increases in size and by more stabilizing dispersion interactions promoted by the larger X. In addition, there is an overlooked covalent component stemming from metal-metal and ligand-ligand donor-acceptor interactions. Thus, at variance with the currently accepted picture, the d-d metallophilicity is attractive, and the formation of [M(CO)X] dimers is not a purely dispersion-driven phenomenon.
我们使用ZORA-BLYP-D3(BJ)/TZ2P理论水平的色散校正密度泛函理论，对平面正方形[M(CO)X]配合物（M = Ni、Pd、Pt；X = Cl、Br、I）二聚体中的闭壳层d-d亲金属相互作用进行了量子化学分析。我们的目的是通过分析M和X变化时的趋势，揭示[X(CO)M]⋯[M(CO)X]键合机制的本质。我们的分析表明，当M的尺寸增大时，[M(CO)X]二聚体的形成受到越来越稳定的静电相互作用的促进，而较大的X则促进了更稳定的色散相互作用。此外，还存在一个被忽视的共价成分，它源于金属-金属和配体-配体供体-受体相互作用。因此，与目前公认的情况不同，d-d亲金属性是有吸引力的，[M(CO)X]二聚体的形成不是纯粹的色散驱动现象。
