Synthesis, Structural, and Theoretical Analysis of Ru4(CO)12(μ-PF2)(μ4-P):  Is the μ4-P Atom a Three-Electron or a Five-Electron Donor?

Synthesis, Structural, and Theoretical Analysis of Ru4(CO)12(μ-PF2)(μ4-P):  Is the μ4-P Atom a Three-Electron or a Five-Electron Donor?

The X-ray molecular structure of Ru4(CO)12(μ-PF2)(μ4-P) exhibits a rather open Ru4 butterfly with no Ru−Ru bond along the butterfly hinge, which is bridged by a μ-PF2 ligand. The μ4-P atom unsymmetrically bridges the Ru4 butterfly with two very different Ru−P−Ru angles:  148.71(15) and 95.43(10)°. T...

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Veröffentlicht in:Organometallics 2001-10, Vol.20 (22), p.4469-4475
Hauptverfasser: Kahlal, Samia, Wang, Weibin, Scoles, Ludmila, Udachin, Konstantin A, Saillard, Jean-Yves, Carty, Arthur J
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container_end_page 4475
container_issue 22
container_start_page 4469
container_title Organometallics
container_volume 20
creator Kahlal, Samia
Wang, Weibin
Scoles, Ludmila
Udachin, Konstantin A
Saillard, Jean-Yves
Carty, Arthur J
description The X-ray molecular structure of Ru4(CO)12(μ-PF2)(μ4-P) exhibits a rather open Ru4 butterfly with no Ru−Ru bond along the butterfly hinge, which is bridged by a μ-PF2 ligand. The μ4-P atom unsymmetrically bridges the Ru4 butterfly with two very different Ru−P−Ru angles:  148.71(15) and 95.43(10)°. The peculiar coordination mode of the μ4-P atom raises the question of how many electrons (three or five) it gives to the metal framework. DFT calculations on the [Ru4(CO)12(μ-PF2)(μ4-P)]2-/0/2+ series indicate that the phosphorus atom is better described as being a three-electron donor. Its unexpected pyramidalization is the result of atomic size and of the pinch effect of the μ-PF2 ligand. The bonding in this cluster has been analyzed and compared to that of the related series [Ru4(CO)12(μ-PF2)(μ4-N)]0/2+ and the [M4(CO)12(μ4-E)]-/3- (M = Fe, Ru; E = N, P). A very good agreement between the optimized geometries and the available X-ray data is observed.
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title Synthesis, Structural, and Theoretical Analysis of Ru4(CO)12(μ-PF2)(μ4-P):  Is the μ4-P Atom a Three-Electron or a Five-Electron Donor?
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