Bridging Coordination of Vinylarenes to Pd3 - or Pd4 Cluster Sites.

  title={Bridging Coordination of Vinylarenes to Pd3 - or Pd4 Cluster Sites.},
  author={Yuki Ishikawa and Seita Kimura and Koji Yamamoto and Tetsuro Murahashi},
  volume={23 57},
Though the M3 - or M4 face of palladium clusters may serve as the active binding site of substrates, it has been difficult to elucidate their substrate binding modes in solution. Here, it was proved that a soluble Pd3 - or Pd4 sheet cluster accommodates vinylarenes at its bridging coordination site in an unusual mode in palladium chemistry; that is, for the former, the coordination of the arene moiety precedes that of olefin moiety; for the latter, vinylarene coordinates to a distorted Pd4… 
11 Citations
Thiophene- and Selenophene Binding at a Pd3 Cluster Site.
Thiophene or selenophene is accommodated stably at a Pd 3 site supported by a backside μ3 -cyclooctatetraene ligand through the face-capping μ 3 -coordination and forms a unique spiro-type Pd 5 cluster.
Bimodal coordination of fused arenes to a Pd3 cluster site.
It is reported that a cyclooctatetraene-supported Pd3 cluster accommodates anthracene and tetracene in an oxidative π-addition manner, whereas triphenylene and fluoranthene are accommodated in a ρ-coordination manner.
Three-Dimensional Sandwich Nanocubes Composed of 13-Atom Palladium Core and Hexakis-Carbocycle Shell.
Coordination of cyclic unsaturated hydrocarbons to transition metal generally gives bis-ligated sandwich complexes, which are a fundamental class of organometallic compounds. This sandwich structure
Construction of a Planar Tetrapalladium Cluster by the Reaction of Palladium(0) Bis(isocyanide) with Cyclic Tetrasilane
The planar tetrapalladium cluster Pd4{Si(iPr)2}3(CNtBu)4 (4) was synthesised in 86% isolated yield by the reaction of palladium(0) bis(isocyanide) Pd(CNtBu)2 with octaisopropylcyclotetrasilane (3).
Synthesis of Surface-Analogue Square-Planar Tetranuclear Nickel Hydride Clusters and Bonding to μ4-NR, -O and -BH Ligands.
Tetranuclear Ni complexes were synthesized with bonding to BH, NR, and O in atypical surface-like geometries and the solid-state structure of 5 was determined using both X-ray and neutron diffraction.
The partial dehydrogenation of aluminium dihydrides
The reactions of a series of β-diketiminate stabilised aluminium dihydrides with ruthenium bis(phosphine), palladium bis(phosphine) and palladium cyclopentadienyl complexes is reported.
Exceeding Metal Capacity in Sandwich Complexes: Ligand-unsupported Docking of Extra Metal Moieties at Edges of a Metal Sheet Sandwich Complex.
It is found that the M-M edge bonds in a metal sheet sandwich complex provide a ligand-unsupported docking site for extra metal moieties, allowing expansion of metal-capacity in sandwich complexes.
Dimensionality Expansion of a Butterfly Shaped Pd4 Framework: Constructing Edge-Sharing Pd6 Tetrahedra.
The rational synthesis of a 2D butterfly shaped Pd4 framework and 3D edge-sharing Pd6 tetrahedra by treatment of easily available organosilicon compounds with Pd(CNtBu)2 is reported, where the diphenylsilylene moiety serves as the key component to generate the butterfly structure of the Pd 4 clusters in 2.


Modulation of benzene or naphthalene binding to palladium cluster sites by the backside-ligand effect.
The present results imply that the ligand design of theMetal clusters, especially for the backside ligand of the metal cluster site, is crucial to acquire a desired reactivity of metal clusters.
Bridging π-coordination of pyrrole and indole over a Pd(I)-Pd(I) bond.
π-Coordination of pyrrole or indole which lack a chelating functionality to a dinuclear Pd(I)-Pd(I) center is revealed. The dinuclear sandwich Pd(I)-Pd(I) complexes of pyrrole, N-methylpyrrole, or
Cooperative carbon-atom abstraction from alkenes in the core of a pentanuclear nickel cluster
Interest in surface-mediated chemistry has led to the design of small molecule models for surfaces, which provide mechanistic insight and have practical applications. Now, the cooperative behaviour
Synthesis and ligand substitution reactions of a homoleptic acetonitrile dipalladium(I) complex
The first homoleptic nitrile dipalladium(I) complex [Pd2(CH3CN)6][BF4]2 is prepared; the CH3CN ligand undergoes facile displacement by phosphine or bidentate nitrogen ligands while the Pd–Pd bond
Reductive coupling of metal triangles in sandwich complexes.
Both monomer and dimer of cycloheptatriene complexes were structurally determined by X-ray crystallographic analyses.
Synthesis and structural characterisation of [Pd4(μ3-CH)(μ-Cl)3(PBut3)4]: a tetrahedral palladium cluster with a μ3-methylidyne ligand
The compound [Pd4(µ3-CH)(µ-Cl)3(PBut3)4] has been synthesised from [Pd2(dba)3](dba = dibenzylideneacetone), PBut3 and CHCl3 and characterised spectroscopically and by single-crystal X-ray analysis;