Detection of Pd(III) and Pd(IV) Intermediates during the Aerobic Oxidative C–C Bond Formation from a Pd(II) Dimethyl Complex

The dimethyl PdII complex (MeN4)PdIIMe2 (MeN4 = N,N′-dimethyl-2,11-diaza[3,3](2,6)pyridinophane) is readily oxidized by dioxygen in the presence of protic solvents to selectively eliminate ethane. UV–vis, EPR, ESI-MS, and NMR studies reveal the formation of several PdIII and PdIV intermediates durin...

Full description

Saved in:
Bibliographic Details
Published in:Organometallics 2012-09, Vol.31 (18), p.6690-6696
Main Authors: Tang, Fengzhi, Zhang, Ying, Rath, Nigam P, Mirica, Liviu M
Format: Article
Language:English
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 dimethyl PdII complex (MeN4)PdIIMe2 (MeN4 = N,N′-dimethyl-2,11-diaza[3,3](2,6)pyridinophane) is readily oxidized by dioxygen in the presence of protic solvents to selectively eliminate ethane. UV–vis, EPR, ESI-MS, and NMR studies reveal the formation of several PdIII and PdIV intermediates during the aerobically induced C–C bond formation reaction, including the key intermediate [(κ3-MeN4)PdIVMe3]+, which leads to ethane elimination. The latter complex was also synthesized independently and structurally characterized to reveal a distorted octahedral geometry that is proposed to promote facile reductive elimination. Overall, this study represents a rare example of aerobic oxidation of an organometallic PdII precursor that leads to a well-defined PdIV species, which undergoes selective C–C bond formation under ambient conditions.
ISSN:0276-7333
1520-6041
DOI:10.1021/om300752w