Kurzmitteilung / Short Communication P  C Bond Activation and η⁴‐Coordination of Arene: X‐ray Crystal Structure of a Dinuclear μ‐Phosphido μ‐η²:η²‐Phenoxo Zwitterionic Complex of Palladium Trapping an Aggregate of Three Hydrogen‐Bonded Phenol Molecules

Abstract

Pd[P(tBu)3]2 reacts photochemically with an excess of phenol in n‐hexane to give the dinuclear complex [{P(tBu)2H}2Pd2{μ‐P(tBu)2}(μ‐η2:η2‐C6H5O)]  3 C6H5OH (1); X‐ray crystallography shows a linear chain of three phenol molecules hydrogenbonded to the phenoxide ligand which is η4‐coordinated to the Pd2 framework. The π coordination of the phenoxide ring is retained in solution, as evidenced by 1H‐NMR spectroscopy.

Synthesis of two novel dinuclear palladium(i) complexes and studies of their catalytic activity in amination reactions

“…Complexes where an arene is p-coordinated to a Pd I -Pd I unit are rare. [7][8][9][10][11] In contrast to the previously reported examples, to the best of our knowledge, 2 and 3 are the first structurally characterised compounds where an arene is coordinated to a Pd I -Pd I unit in a m 2 -h 3 :h 3 fashion. 12 The solid state structures of 2 and 3 are consistent with the spectroscopic and analytical characterization of the bulk materials.…”

The surprisingly facile formation of Pd(i)–phosphido complexes from ortho-biphenylphosphines and palladium acetate

“…13 Similarly, phosphide-bridged Pd(I) dimers such as 7 are known, 14 but the phosphide-bridged, arene-bridged motif displayed by the complexes 4 is very rare with, to the best of our knowledge, only one structurally-characterised example (8) reported previously. 15 The Pd-Pd bond-lengths in 4a and b (2.6246(9) and 2.6076(4) Å respectively) fall in the range of those reported for one-atom bridged Pd(I) dimers. 16,17 Scheme 2.…”

Theoretical Overview of Pd(I) and Pt(I) Dimers with Bridging Phosphido Ligand(s)

“…This selection is limited to 16-electron metal centers with planar coordination. The gross features of the selected compounds 1 − 25 (their identities are listed Table ) − can be described as follows.…”