Structural characterization of 1,1,1,2,2,2,3,3,3-nonacarbonyl-1,2-μ-iodo-1,2,3-[μ3-(phenylpyridylphosphido)-μ-P,N]-triangulo-triruthenium

The compound [Ru,(CO),,] reacts at room temperature in tetrahydrofuran with tri(2-pyridyl)phosphine, P(2-C,H,N),, when catalysed by [N(PPh,),]CI, to give a product derived by cleavage of a phosphorus-2-pyridyl bond, [Ru,(p-2-C,H,N){p3-P(2-C5H,N),}(CO),] 1. No simple substitution compounds could be isolated. The likely intermediates [Ru,(CO),{P(~-C,H,N)~}] ( n = 10 and/or 11 ) spontaneously decarbonylate while a 2-pyridyl group migrates from phosphorus to ruthenium atoms. A similar reaction using phenyldi(2-pyridy1)phosphine. PPh(2-CSH4N),, leads to the competitive transfer of 2-pyridyl and phenyl groups to give almost equal quantities of two products, [Ru3(p-2-C,H,N){b-PPh(2-C,H,N)}-(CO),] and [Ru3(p-PhCO){~-P(2-C5H4N)30,1. The crystal structure of 1 shows that the 2-pyridyl group that has migrated bridges two ruthenium atoms with no Ru-Ru bond between them and that the di(2-pyridy1)phosphido ligand is triply bridging with one nitrogen co-ordinated and one free. As in the reported reaction of [RuJCO),,] with PPh2(2-C,H,N) to give [Ru3(p-PhCO){~-PPh(2-C,H,N)}( CO),], the reason why P-C bond cleavage occurs under remarkably mild conditions and the mechanism of the processes have still to be determined.

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Structural characterization of 1,1,1,2,2,2,3,3,3-nonacarbonyl-1,2-μ-iodo-1,2,3-[μ3-(phenylpyridylphosphido)-μ-P,N]-triangulo-triruthenium

Cited by 2 publications

References 4 publications

Trinuclear Clusters of Ruthenium and Osmium: (i) Introduction and Simple Neutral, Anionic and Hydrido Clusters

Trinuclear Clusters of Ruthenium and Osmium: (i) Introduction and Simple Neutral, Anionic and Hydrido Clusters

Cleavage of phosphorus–phenyl and phosphorus-2-pyridyl bonds in the reactions of mixed phenyl-(2-pyridyl) phosphines with [Ru₃(CO)₁₂]

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Structural characterization of 1,1,1,2,2,2,3,3,3-nonacarbonyl-1,2-μ-iodo-1,2,3-[μ3-(phenylpyridylphosphido)-μ-P,N]-triangulo-triruthenium

Cited by 2 publications

References 4 publications

Trinuclear Clusters of Ruthenium and Osmium: (i) Introduction and Simple Neutral, Anionic and Hydrido Clusters

Trinuclear Clusters of Ruthenium and Osmium: (i) Introduction and Simple Neutral, Anionic and Hydrido Clusters

Cleavage of phosphorus–phenyl and phosphorus-2-pyridyl bonds in the reactions of mixed phenyl-(2-pyridyl) phosphines with [Ru3(CO)12]

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Cleavage of phosphorus–phenyl and phosphorus-2-pyridyl bonds in the reactions of mixed phenyl-(2-pyridyl) phosphines with [Ru₃(CO)₁₂]