An Unusual Palladium Complex Involved in an Unusual Rearrangement of Ortho-Palladated Aryldithioacetals

The reaction of 1 with Pd(dba)2, Tl(TfO) and PPh3 in 1:1:1:2 molar ratios to give 3 implicates (i) an oxidative addition reaction, (ii) a rearrangement involving the cleavage of one HC−S bond and formation of an aryl-S bonds, and (iii) coordination of the Pd(PR3)2 group with a ligand intermediate be...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the American Chemical Society 2002-04, Vol.124 (15), p.3848-3849
Main Authors: Vicente, José, Abad, José-Antonio, Hernández-Mata, Francisco S, Jones, Peter G
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
Kinetics and mechanisms
Organic chemistry
Reactivity and mechanisms
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The reaction of 1 with Pd(dba)2, Tl(TfO) and PPh3 in 1:1:1:2 molar ratios to give 3 implicates (i) an oxidative addition reaction, (ii) a rearrangement involving the cleavage of one HC−S bond and formation of an aryl-S bonds, and (iii) coordination of the Pd(PR3)2 group with a ligand intermediate between η2-[ArCHS(+)To] and κ2-C,S-ArCH(-)STo, which requires the consideration of 3 as intermediate between a Pd(0) and a Pd(II) complex. The coordination of the ligand as a chelating three-membered ring, instead of the expected five-membered ring involving C(10) and S(1), and the partial intramolecular redox process are explained as a consequence of the transphobia of the pair of ligands Ph3P/CH(STo)Ar.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja0175035