The First Structural Characterization of a [2.2]PHANEPHOS−Transition-Metal Complex:  Structure of rac-[Pd(4,12-bis(diphenylphosphino)[2.2]paracyclophane)Cl₂]

Abstract

The solid-state structure of the [2.2]PHANE-PHOS-transition-metal complex rac- [Pd(4,[2.2]paracyclophane)Cl 2 ] has been established by single-crystal X-ray diffraction. The P-Pd-P bite angle is ideally suited to catalytic processes such as carbon-carbon cross-coupling reactions, which involve reductive elimination as the rate-determining step.

Unprecedented One‐Pot Reaction towards Chiral, Non‐Racemic Copper(I) Complexes of [2.2]Paracyclophane‐Based P,N‐Ligands

“…The molecular structure of 15 confirms the suggested mononuclear palladium(II) complex with a slightly distorted square‐planar coordination geometry around the palladium center that possesses cis ‐configuration (Figure ). This cis ‐configuration was also observed for the respective PhanePhosPdCl 2 complex, although the PhanePhos ligand shows the distinctly larger bite angle of 103.69° compared to 95.40° for the P,N ‐ligand in 15 . The bond lengths are comparable to other reported dichloropalladium(II) complexes of P,N ‐ligands, and also show a longer Pd−Cl bond trans to phosphorus.…”

Application of SDP Ligands for Pd‐Catalyzed Allylic Alkylation

“…The bond angle of P À Pd À P is 96.018, which is greater than that of PdCl 2 [(R)-BINAP] (92.698), [16] and smaller than that of PdCl 2 (PhanePhos) (103.698). [17] The Pd À P distances (2.241 and 2.282 ä) and Pd À Cl distances (2.330 and 2.351 ä) are in the typical ranges for dichloropalladium complexes bearing diphosphine ligands. [18] Asymmetric Allylic Alkylation Palladium-catalyzed asymmetric C À C bond forming reactions with allylic compounds have been extensively investigated, [19] especially the palladium-catalyzed allylic alkylation of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate.…”

Planar Chiral Phosphines Derived from [2.2]Paracyclophane

“…It is unclear why PhanePhos is so effective in rhodium and ruthenium‐mediated hydrogenations. Analysis of the X‐ray crystallographic structure of the diphosphine dioxide derivative,6 the palladium,27 and the platinum28 complexes of PhanePhos does not offer much enlightenment. In the phosphine oxide, the distance between the two phosphorus atoms is 4.8 Å, which can readily accommodate the two P‐Rh bond distances.…”