Activation of Hydrogen by Palladium(0): Formation of the Mononuclear Dihydride Complextrans‐[Pd(H)₂(IPr)(PCy₃)]

Abstract

An even split: In sharp contrast with the general behavior of Pd0 complexes, [Pd(IPr)(PCy3)] is able to activate the HH bond. The resulting trans‐[Pd(H)2(IPr)(PCy3)] is the first isolated mononuclear dihydride palladium compound. Its formation is supported by multinuclear NMR spectroscopy, density functional calculations, and X‐ray diffraction studies. The stability and reactivity of this new species are examined.magnified image

Stabilization of Nanoparticles Produced by Hydrogenation of Palladium–N-Heterocyclic Carbene Complexes on the Surface of Graphene and Implications in Catalysis

“…28,29 In this article, we discuss the preparation of palladium NPs (Pd-NPs) containing NHC ligands by the decomposition of well-defined organometallic complexes. 30−32 The catalytic properties of the Pd-NPs are evaluated in the hydrogenation of alkynes as a benchmark reaction. We describe the influence of graphene as a support for the Pd-NPs and the potential benefits in catalytic applications.…”

The partial dehydrogenation of aluminium dihydrides

“…The 2 J P-H coupling constant of 84 Hz is signicantly larger than the typical range of 0-20 Hz expected for Pd complexes with a cis relationship between the hydrogen and phosphorus atoms. 29,30 Nevertheless, this J value is still smaller than the range of 150-200 Hz established for crystallographically characterised square-planar palladium complexes involving a trans 2 J P-H coupling. [31][32][33] An equivalent reaction using 1f also gave a low intensity broad doublet resonance at d ¼ À0.61 ppm ( 2 J H-P z 85 Hz) in the low temperature 1 H NMR spectrum at 193 K which resolved to a broad singlet in the 1 H{ 31 P} NMR spectrum (see ESI †).…”

Synthesis and characterization of Pd(IMe)2, and its reactivity by C–S oxidative addition of DMSO

“…Given the sterically unimposing apparent structure of 2a, we considered the possibility of misidentifying in 2a a dihydride trans-Pd(H) 2 IMe 2 . The multiple CH.Pd contacts observed in the crystal structure of 2a do leave some room for two potential transhydrides in the plane orthogonal to the IMeePdeIMe vector: when placed at PdeH ¼ 1.60e1.83 Å [15,16], :HePdeH ¼ 180 , and :HePdeC ¼ 90 in each of the two independent molecules, their shortest non-bonded contacts e all to IMe hydrogens [14] e maximize over the dihedral :HePdeCeN ¼ 0e180 orientation of the trans-HePdeH unit to 1.94 Å (Fig. S1 [17]).…”