Novel reactions of metal-metal bonds. Reactions of Pd2{C6H5)2PCH2P(C6H5)2}2Cl2 with acetylenes, olefins, and isothiocyanates

Abstract

Acetylene (II) reagieren mit den Pd‐ Komplexen (I) zu den Komplexen (III) mit A‐Gerüst‐Struktur, die mittels IR‐ sowie 1H‐ und 31P‐NMR‐Spektroskopie charakterisiert werden.

A new synthesis for thermolabile low-valent palladium complexes by electron transfer reactions from nickel(0) to palladium(II) compounds

“…This suggests that a redox reaction has occurred in which two electrons were transferred from Ni(0) to two Pd(II) centres accompanied by the exchange of cod and two chloride ligands (Eq. (1) It is interesting to note that the known dimeric Pd(I) complexes usually contain strong ligands with P-or Ndonor atoms or mixed N-P chelate ligands [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. In many of them the Pd centres are connected by bridging ligands.…”

Properties of [Pd2X2(dppm)2] (X = Cl, SnCl3, dppm = Bis(diphenylphosphino)methane) complexes on porous vycor glass

“…[20][21][22][23][24] In general, color changes upon gas exposure have been observed for all samples, indicating insertion of gas molecules into the Pd-Pd bonds. Evidences for the insertion reactions were provided by UV-Visible spectroscopy and after gas exposure new bands can be observed in Figure 5.…”

“…Pd-Pd bond lengths were found to increase by 0.5 Å after insertion of molecules with withdrawing groups such as CO, SO 2 , methylene groups, and isocyanides. [20][21][22][23][24][25] Adducts with Aframe structures such as [Pd 2 Cl 2 (µ-SO 2 )(dppm) 2 ] and [Pd 2 Cl 2 (µ-CO)(dppm) 2 ] can be prepared by bubbling the gases into solutions of the compound [Pd 2 Cl 2 (dppm) 2 ], with observable color changes.As far as the reactivity of single bonded Pd 2 moieties are concerned attempts previously reported to immobilize similar compounds onto polystyrene for application such as separation of gases were unsuccessful due to steric demands. 25 We were further interested in studying the reactions of the immobilized species with CO and SO 2 gases, having reported preliminary results for porous Vycor glass.…”

“…These new bands appear at the same wavenumbers observed when the reactions are carried out in solution. [20][21][22][23][24] Additional characterization, such as Raman spectrosopy, was not possible owing to the dilute character of the Aframe adducts in the glass. However, measurements of the intensities of color change by UV-Visible spectroscopy may be the basis for use of this material in gas detection.…”

“…Pd-Pd bond lengths were found to increase by 0.5 Å after insertion of molecules with withdrawing groups such as CO, SO 2 , methylene groups, and isocyanides. [20][21][22][23][24][25] Adducts with Aframe structures such as [Pd 2 Cl 2 (µ-SO 2 )(dppm) 2 ] and [Pd 2 Cl 2 (µ-CO)(dppm) 2 ] can be prepared by bubbling the gases into solutions of the compound [Pd 2 Cl 2 (dppm) 2 ], with observable color changes.…”