Bridging Coordination of Vinylarenes to Pd₃‐ or Pd₄ Cluster Sites

Abstract

Though the M - or M 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 Pd - or Pd 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 Pd sheet through oxidative π-addition of its styrene moiety.

Mechanistic Insight into H/D Exchange by a Pentanuclear Ni–H Cluster and Synthesis and Characterization of Structural Analogues of Potential Intermediates

“…The past decade has seen several reports of transition metal clusters , undergoing unprecedented bond transformations with traditionally inert bonds, − including the activation of C–C bonds in hydrocarbons such as benzene , and ethylene . This has spurred on the rational design of transition metal clusters and polynuclear complexes, − in an attempt to access similar cooperative reactivity. Interactions among proximal late transition metal centers could be envisioned to facilitate metal surface-like transformations.…”

Construction of a Planar Tetrapalladium Cluster by the Reaction of Palladium(0) Bis(isocyanide) with Cyclic Tetrasilane

“…To overcome these drawbacks, a new methodology called template synthesis has recently been introduced [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28]. In this method, the products are synthesized by clustering multiple metal atoms To overcome these drawbacks, a new methodology called template synthesis has recently been introduced [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28].…”

“…In this method, the products are synthesized by clustering multiple metal atoms To overcome these drawbacks, a new methodology called template synthesis has recently been introduced [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28]. In this method, the products are synthesized by clustering multiple metal atoms on the template.…”

“…Using this synthetic strategy, many transition metal clusters having 1D chain-like structures have been prepared by employing polyenes [10][11][12][13], multidentate phosphines [14][15][16][17], and nitrogen-containing compounds as templates [18][19][20][21][22]. Similarly, the use of (poly)cyclic aromatic hydrocarbons as a template led to the formation of metal clusters with 2D sheet-like structures [23][24][25][26][27][28]. However, only a limited number of 2D sheet-like clusters have been prepared, due to the lack of suitable template molecules.…”

The partial dehydrogenation of aluminium dihydrides

“…Complexes with four or more Pd centres in this diamond conguration are generally not planar, those close to planarity are forced so by being sandwiched between planar aromatic ligands. [48][49][50][51][52] A few high nuclearity clusters supported by main group ligands are known, including triangular (tris)platinum complexes and planar (tetrakis)palladium complexes. In the latter a single Pd centre is connected to three Pd and Si or Ge atoms.…”