Simulation Investigation of Bis(pentaphospholyl) Metallocenes of Fe, Ru, and Os

Abstract:

The structures, stabilities, and bonding features of neutral M(η⁵-P₅)₂ (M = Fe, Ru, and Os) and cationic M(η⁵-P₅)+ have been investigated using density functional theory (DFT) (hybrid B3LYP and pure BP86 methods). The eclipsed (D5h) structure has been predicted to be the global minimum for this triad bis(pentaphospholyl) metallocenes, and the staggered (D5d) structure to be the rotational transition state. The distances between the metal and cyclo-P5 center in bis(pentaphospholyl) metallocenes are longer than in the corresponding M(η⁵-P₅)+ by 0.28-0.38 Å. The M(η⁵-P₅)+ complexes may be tighter binding with the shorter metal-ring distances, the possible reason is that there being stronger metal-ring π interactions in M(η⁵-P₅)+ than in M(η⁵-P₅)₂, even though latter satisfies the 18-electron rule. The electron densities are found to accumulate at the metal centers, this novel situation may have an impact on the mechanism of some potential catalysis reactions.

• Periodical: Advanced Materials Research (Volume 763)
• Pages: 139-142
• DOI: https://doi.org/10.4028/www.scientific.net/AMR.763.139
• Online since: September 2013
• Authors: Liang Fa Gong, Qi Qun Cao, Jia Wen, Hua Rong, Ming Lan Ge
• Keywords: Bis(Pentaphospholyl) Metallocenes, Density Functional Theory (DFT), Sandwich

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