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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DOIResolve DOI: http://doi.org/10.1021/om010352u
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TypeArticle
Journal titleOrganometallics
ISSN0276-7333
Volume20
Issue22
Pages44694475; # of pages: 7
AbstractThe X-ray molecular structure of Ru4(CO)12(-PF2)(4-P) exhibits a rather open Ru4 butterfly with no Ru-Ru bond along the butterfly hinge, which is bridged by a -PF2 ligand. The 4-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 4-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(-PF2)(4-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 -PF2 ligand. The bonding in this cluster has been analyzed and compared to that of the related series [Ru4(CO)12(-PF2)(4-N)]0/2+ and the [M4(CO)12(4-E)]-/3- (M = Fe, Ru; E = N, P). A very good agreement between the optimized geometries and the available X-ray data is observed.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedNo
Identifier10309731
NPARC number12337960
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Record identifierf06595d7-f809-4615-8f3c-72d15a82a2f9
Record created2009-09-10
Record modified2016-05-09
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